CN102275350B - Namometer SiO2-doped polymer laminated film and preparation method thereof - Google Patents
Namometer SiO2-doped polymer laminated film and preparation method thereof Download PDFInfo
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- CN102275350B CN102275350B CN 201110119263 CN201110119263A CN102275350B CN 102275350 B CN102275350 B CN 102275350B CN 201110119263 CN201110119263 CN 201110119263 CN 201110119263 A CN201110119263 A CN 201110119263A CN 102275350 B CN102275350 B CN 102275350B
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Abstract
The invention discloses a namometer SiO2-doped polymer laminated film and a preparation method thereof. The preparation method of the polymer laminated film comprises the steps of: doping and modifying nanometer SiO2 particles and coating the particles on a substrate, and then further depositing a 0.5-micron to 10-micron thin film on the modified nanometer SiO2 particles to obtain the polymer laminated film. According to the invention, the heat stability and mechanical performance of the polymer laminated film can be improved.
Description
Technical field
What the present invention relates to is a kind of material and method of micro-electromechanical system field, specifically a kind of dopen Nano SiO
2Polymer composite film and preparation method thereof.
Background technology
Parylene (Parylene) film is one of polymeric material that is most widely used in the world at present, and it is a kind of thermoplastic macromolecule material of high-crystallinity.Up to the present Parylene family has formed the close Multiple Type of series of properties, usually adopts chemical vapour deposition technique preparation (Gorham method).Parylene C is with a polymer that hydrogen atom obtains on a chlorine atom replacement paraxylene phenyl ring.It has excellent biocompatibility, gas and steam barrier property, and optical property, electrical insulating property and the characteristic such as anticorrosive are the most effective moisture prooves, mould proof and high-frequency unit barrier material.Parylene C film is multiplex in the encapsulation of minute yardstick electronic device and little manufacture fields such as biocompatibility protection of vivo implantation type device at present.
But along with the development of vivo implantation type device research, more and more higher to the demand of biocompatible materials, therefore, the problem such as in the use procedure of ParyleneC film heat endurance and mechanical strength be low is obvious gradually.U.S. SCS company has announced the Parylene HT of up-to-date development recently, after this kind polymer is compared Parylene C film forming, high-temperature resistance has had significant raising, but this kind material price costliness, the introducing equipment cost is very high, and long by the new deposition raw material of developmental research costly construction cycle while that meets the demands not only, can't satisfy the quick application demand to new functional material.Therefore in the urgent need to a kind of low cost, technique simply prepares the method for functional Parylene C film.
Nanometer SiO
2Owing to having many premium properties, as small-size effect, photoelectric characteristic has high strength under high temperature, high tenacity, and high stability, preparation is simple, thereby is used widely.By physics or chemical method make nanometer SiO2 and organic matter compound, can prepare multi-functional composite.At present, nanometer SiO
2Composite has caused the attention of the U.S., Britain, Germany and a plurality of countries such as Japanese, makes nanometer SiO
2Composite becomes one of study hotspot of current nano composite material.
Find through the literature search to prior art, Seshadri Ganguli etc. are at Journal of Vacuum Science ﹠amp; Technology is (6) A.15: 3138-3142,1997 write articles " Improved growth and thermal stability of Parylene films " (growth of Parylene film and thermal stability improve).Its principle is by the raising chamber pressure, reduces base reservoir temperature, and then improves growth rate and the polymer molecule weight of film, thereby improve the heat endurance of film.But high pressure can reduce the quality of deposit film, reduces base reservoir temperature and need to increase cooling device in original vacuum equipment, has greatly improved cost.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of dopen Nano SiO is provided
2Polymer composite film and preparation method thereof, by the nanometer SiO after doping vario-property
2Particle improves heat endurance and the mechanical performance of this film.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of dopen Nano SiO
2The preparation method of polymer composite film, by to nanometer SiO
2Particle carries out doping vario-property and is coated in substrate, then the further nanometer SiO after modification
2Deposit the film of 0.5～10 micron on particle, obtain polymer composite film.
Described doping vario-property refers to: will be scattered in the nanometer SiO in polar solvent
2Particle obtains mix oven dry with silane coupler solution after;
Described nanometer SiO
2Particle refers to: through the nanometer SiO of 100 ℃ of dry 24h in electric heating constant-temperature blowing drying box
2Particle.
Described polar solvent is the solution that absolute ethyl alcohol and deionized water are mixed with the volume ratio of 1: 1
Described dispersion refers to: ultrasonic dispersion 2h
Described silane coupler solution refers to: be dissolved in the KH570 in absolute ethyl alcohol, its consumption is nanometer SiO
25% of mass particle.
Described mixing oven dry refers to: after 75 ℃ of lower constant temperature stir 4h, product is carried out the centrifugation of three circulations, ultrasonic dispersion and suction filtration successively process.
Described coating refers to: will be scattered in the nanometer SiO after the modification in absolute ethyl alcohol
2Particle is by being sprayed onto substrate or adopting the mode that czochralski method immerses substrate to realize.
Described substrate is silicon chip, sheet glass or sheet metal.
Described deposition refers to: will apply by the nanometer SiO after modification
2Deposit cavity is put in the substrate of particle, by the chemical vapour deposition (CVD) mode with Payrlene C dimer 80～170 ℃ of time evaporations, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make Parylene C film, the pressure in whole deposition process is below 8 millitorrs.
The dopen Nano SiO that the present invention prepares by said method
2Polymer composite film, its component is: Parylene C film and be scattered in nanometer SiO in Parylene C film
2Particle.
Nanometer SiO by doping vario-property in the present invention
2Technique, thin polymer film heat endurance and the mechanical performance of preparation are very significantly improved, and cardinal principle is by silane coupler modified, nanometer SiO
2The silane key of particle surface grafting forms organic layer, effectively stops nanometer SiO
2The reunion of particle, and improve active force between itself and polymer P arylene C monomer molecule, thus improve heat endurance and the mechanical performance of film.
Description of drawings
Fig. 1 is Parylene C and the nanometer SiO that embodiment 3 makes
2The SEM photo of laminated film.
Fig. 2 is pure Parylene C film and the Parylene C/SiO that embodiment 3 makes
2The TGA correlation curve of laminated film.
Fig. 3 is the pure Parylene C film that makes and the Parylene C/SiO of sandwich
2The DMA correlation curve of laminated film.
The specific embodiment
The below elaborates to embodiments of the invention, and the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) nanometer SiO
2The modification of particle
Particle is put into 100 ℃ of dry 24h of electric heating constant-temperature blowing drying box.Preparation absolute ethyl alcohol and deionized water (1: 1) mixed solution 30mL pour in beaker, add 0.5g nanometer SiO
2, pour in there-necked flask after ultrasonic dispersion 2h, (KH570 is SiO to get silane coupler
2Quality 5%) be dissolved in the 20mL absolute ethyl alcohol, add in there-necked flask after fully stirring, stir 4h at 75 ℃ of lower constant temperature.At last the gained emulsion is carried out high speed centrifugation separation, ultrasonic dispersion, suction filtration, repeat 3 times, the nanometer SiO after the oven dry modification
2, vacuum storage is standby.
(2) the nanometer SiO after the coating modification
2Particle
With the nanometer SiO after modification
2Particle and absolute ethyl alcohol mixed by 1: 150, ultrasonic 30min, and the substrate of employing is the single-sided polishing silicon chip.Stable turbid liquid spraying is made its submergence to the burnishing surface of silicon chip, or adopt czochralski method that silicon chip is mentioned from suspension by given pace, then use the small air-flow of high pressure nitrogen with silicon wafer blow-drying, obtain the nanometer SiO of the uniform modification of surface coating one deck
2The silicon chip of particle.
(3) preparation of Parylene C laminated film
The silicon chip of coating nanometer particle is put into deposit cavity, adopts chemical vapor depsotition equipment, Payrlene C dimer is evaporated in the time of 80～170 ℃, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make Parylene C film.Whole process device pressure is controlled at below 8 millitorrs.This laminated film degradation temperature improves 80～100 ℃, and heat endurance improves.
(1) nanometer SiO
2The modification of particle
Particle is put into 100 ℃ of dry 24h of electric heating constant-temperature blowing drying box.Preparation absolute ethyl alcohol and deionized water (1: 1) mixed solution 30mL pour in beaker, add 0.5g nanometer SiO
2, pour in there-necked flask after ultrasonic dispersion 2h, (KH570 is SiO to get silane coupler
2Quality 5%) be dissolved in the 20mL absolute ethyl alcohol, add in there-necked flask after fully stirring, stir 4h at 75 ℃ of lower constant temperature.At last the gained emulsion is carried out high speed centrifugation separation, ultrasonic dispersion, suction filtration, repeat 3 times, the nanometer SiO after the oven dry modification
2, vacuum storage is standby.
(2) the nanometer SiO after the coating modification
2Particle
With the nanometer SiO after modification
2Particle and absolute ethyl alcohol mixed by 1: 100, ultrasonic 60min, and the substrate of employing is the single-sided polishing silicon chip.Stable turbid liquid spraying is made its submergence to the burnishing surface of silicon chip, or adopt czochralski method that silicon chip is mentioned from suspension by given pace, then use the small air-flow of high pressure nitrogen with silicon wafer blow-drying, obtain the nanometer SiO of the uniform modification of surface coating one deck
2The silicon chip of particle.
(3) preparation of Parylene C laminated film
The silicon chip of coating nanometer particle is put into deposit cavity, adopts chemical vapor depsotition equipment, Payrlene C dimer is evaporated in the time of 80～170 ℃, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make Parylene C film.Whole process device pressure is controlled at below 8 millitorrs.This laminated film degradation temperature improves 80～110 ℃, and heat endurance improves.
Embodiment 3
(1) nanometer SiO
2The modification of particle
Particle is put into 100 ℃ of dry 24h of electric heating constant-temperature blowing drying box.Preparation absolute ethyl alcohol and deionized water (1: 1) mixed solution 30mL pour in beaker, add 0.5g nanometer SiO
2, pour in there-necked flask after ultrasonic dispersion 2h, (KH570 is SiO to get silane coupler
2Quality 5%) be dissolved in the 20mL absolute ethyl alcohol, add in there-necked flask after fully stirring, stir 4h at 75 ℃ of lower constant temperature.At last the gained emulsion is carried out high speed centrifugation separation, ultrasonic dispersion, suction filtration, repeat 3 times, the nanometer SiO after the oven dry modification
2, vacuum storage is standby.
(2) the nanometer SiO after the coating modification
2Particle
With the nanometer SiO after modification
2Particle and absolute ethyl alcohol mixed by 1: 50, ultrasonic 90min, and the substrate of employing is the single-sided polishing silicon chip.Stable turbid liquid spraying is made its submergence to the burnishing surface of silicon chip, or adopt czochralski method that silicon chip is mentioned from suspension by given pace, then use the small air-flow of high pressure nitrogen with silicon wafer blow-drying, obtain the nanometer SiO of the uniform modification of surface coating one deck
2The silicon chip of particle.
(3) preparation of Parylene C laminated film
The silicon chip of coating nanometer particle is put into deposit cavity, adopts chemical vapor depsotition equipment, Payrlene C dimer is evaporated in the time of 80～170 ℃, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make Parylene C film.Whole process device pressure is controlled at below 8 millitorrs.This laminated film degradation temperature improves 80～120 ℃, and heat endurance improves.
Implementation result
The nanometer SiO of preparation sandwich
2With Parylene C laminated film, be used for the DMA test
(1) nanometer SiO
2The modification of particle
Particle is put into 100 ℃ of dry 24h of electric heating constant-temperature blowing drying box.Preparation absolute ethyl alcohol and deionized water (1: 1) mixed solution 30mL pour in beaker, add 0.5g nanometer SiO
2, pour in there-necked flask after ultrasonic dispersion 2h, (KH570 is SiO to get silane coupler
2Quality 5%) be dissolved in the 20mL absolute ethyl alcohol, add in there-necked flask after fully stirring, stir 4h at 75 ℃ of lower constant temperature.At last the gained emulsion is carried out high speed centrifugation separation, ultrasonic dispersion, suction filtration, repeat 3 times, the nanometer SiO after the oven dry modification
2, vacuum storage is standby.
(2) the nanometer SiO after the coating modification
2Particle
With the nanometer SiO after modification
2Particle and absolute ethyl alcohol mixed by 1: 50, ultrasonic 90min, and the substrate of employing is the single-sided polishing silicon chip.Stable turbid liquid spraying is made its submergence to the burnishing surface of silicon chip, or adopt czochralski method that silicon chip is mentioned from suspension by given pace, then use the small air-flow of high pressure nitrogen with silicon wafer blow-drying, obtain the nanometer SiO of the uniform modification of surface coating one deck
2The silicon chip of particle.
(3) preparation of Parylene C laminated film
The silicon chip of coating nanometer particle is put into deposit cavity, adopts chemical vapor depsotition equipment, Payrlene C dimer is evaporated in the time of 80～170 ℃, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make Parylene C film.Whole process device pressure is controlled at below 8 millitorrs.
(4) preparation of interlayer Parylene C laminated film
Repeat (2) (3) process 4 times, the nanometer SiO of preparation sandwich
2With Parylene C laminated film.The pure film of this laminated film stress ratio improves 10N, and mechanical performance improves.
Claims (4)
1. one kind has doping vario-property nanometer SiO
2The preparation method of polymer composite film, it is characterized in that, by to nanometer SiO
2Particle carries out doping vario-property and is coated in substrate, then the further nanometer SiO after modification
2Deposit the polychlorostyrene of 0.5～10 micron on particle for paraxylene Parylene C film, obtain polymer composite film;
Described doping vario-property refers to: will be scattered in the absolute ethyl alcohol that mixes with the volume ratio of 1:1 and the nanometer SiO in the deionized water mixed solution
2Particle be dissolved in absolute ethyl alcohol, consumption is nanometer SiO
25% silane coupler KH570 of mass particle obtains after mixing oven dry;
Described coating refers to: will be scattered in the nanometer SiO after the modification in absolute ethyl alcohol
2Particle is sprayed onto in substrate or adopts the mode that czochralski method immerses substrate to realize;
Described deposition refers to: will be coated with the nanometer SiO after modification
2Deposit cavity is put in the substrate of particle, by the chemical vapour deposition (CVD) mode, be about to polychlorostyrene for the evaporation 80～170 ℃ time of paraxylene Parylene C dimer, be cracked into monomer in the time of 690 ℃, at last in deposit cavity under normal temperature polymerization make polychlorostyrene for paraxylene Parylene C film, the pressure in whole deposition process is below 8 millitorrs.
2. method according to claim 1, is characterized in that, described nanometer SiO
2Particle refers to: through the nanometer SiO of 100 ℃ of dry 24h in electric heating constant-temperature blowing drying box
2Particle.
3. method according to claim 1, is characterized in that, described mixing oven dry refers to: after 75 ℃ of lower constant temperature stir 4h, product is carried out the centrifugation of three circulations, ultrasonic dispersion and suction filtration successively process.
4. one kind has modification dopen Nano SiO
2Polymer composite film, it is characterized in that, prepare according to the described method of above-mentioned arbitrary claim.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104258473B (en) * | 2014-09-29 | 2016-01-13 | 上海交通大学 | Parylene laminated film that spinning strengthens and preparation method thereof |
| CN107331534A (en) * | 2016-04-28 | 2017-11-07 | 北京纳米能源与系统研究所 | A kind of fibrous ultracapacitor and its preparation method and application |
| CN109517412A (en) * | 2018-11-22 | 2019-03-26 | 北京石油化工学院 | A kind of preparation method of nanometer grade silica coating |
| CN110227349A (en) * | 2019-06-12 | 2019-09-13 | 常州大学 | Based on the nano-silicon dioxide modified blended ultrafiltration membrane and preparation method thereof of functionalization sodium base bentonite and amination |
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| WO1999057330A1 (en) * | 1998-05-01 | 1999-11-11 | Desu Seshu B | Oxide/organic polymer multilayer thin films deposited by chemical vapor deposition |
| US20040229051A1 (en) * | 2003-05-15 | 2004-11-18 | General Electric Company | Multilayer coating package on flexible substrates for electro-optical devices |
| US20050064726A1 (en) * | 2003-09-23 | 2005-03-24 | Jason Reid | Method of forming low-k dielectrics |
| CN101429350A (en) * | 2007-11-08 | 2009-05-13 | 深圳大学 | Method for producing nano-organic/inorganic composite atom resistant oxygen coating |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057330A1 (en) * | 1998-05-01 | 1999-11-11 | Desu Seshu B | Oxide/organic polymer multilayer thin films deposited by chemical vapor deposition |
| US20040229051A1 (en) * | 2003-05-15 | 2004-11-18 | General Electric Company | Multilayer coating package on flexible substrates for electro-optical devices |
| US20050064726A1 (en) * | 2003-09-23 | 2005-03-24 | Jason Reid | Method of forming low-k dielectrics |
| CN101429350A (en) * | 2007-11-08 | 2009-05-13 | 深圳大学 | Method for producing nano-organic/inorganic composite atom resistant oxygen coating |
Non-Patent Citations (6)
| Title |
|---|
| KH570用量对纳米SiO2粒子接枝改性的影响;柳建宏、于杰、何敏、鲁圣军;《胶体与聚合物》;20100331;第28卷(第1期);第19-21页 * |
| 何庆等.真空沉积掺杂制备PARYLENE功能薄膜研究.《真空》.2011,第48卷(第1期),第18-20页. |
| 刘枫、沈军、秦仁喜等.聚对二甲苯/SiO2复合薄膜的制备及光学性能研究.《功能材料与器件学报》.2005,第11卷(第1期),第38-42页. |
| 柳建宏、于杰、何敏、鲁圣军.KH570用量对纳米SiO2粒子接枝改性的影响.《胶体与聚合物》.2010,第28卷(第1期),第19-21页. |
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| 聚对二甲苯/SiO2复合薄膜的制备及光学性能研究;刘枫、沈军、秦仁喜等;《功能材料与器件学报》;20050331;第11卷(第1期);第38-42页 * |
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