CN106987804B - Optical glass micron-sized space debris protecting film - Google Patents
Optical glass micron-sized space debris protecting film Download PDFInfo
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- CN106987804B CN106987804B CN201710196600.3A CN201710196600A CN106987804B CN 106987804 B CN106987804 B CN 106987804B CN 201710196600 A CN201710196600 A CN 201710196600A CN 106987804 B CN106987804 B CN 106987804B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
- C23C14/0611—Diamond
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
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Abstract
The invention discloses a kind of optical glass micron-sized space debris protecting films, including the spring structure, bottom film and nanometer multilayer continuous film being successively set on optical glass surface, spring structure is combined closely on substrate optical glass, it is obtained using glancing angle deposition technology, for buffering the Impact energy of minute fragments;Bottom film is whole continuous film layer, is prepared under argon atmosphere by magnetron sputtering technique;Nano-multilayer film is alternately prepared by DLC film and Al film multilayer, and nano-multilayer film is intended to obtain hardness and toughness has good film, is reduced fragment and is hit the generation for leading to film crack.
Description
Technical field
The invention belongs to space environment effect and protection technology fields, and it is empty to relate in particular to a kind of optical glass micron order
Between fragment protective film.
Background technique
Space Optical System is referred to as the eyes of spacecraft, is spaceship and the essential components of various satellites,
Mainly play a part of investigation, detection and collect cosmic space information, so being payload important on spacecraft.Optics glass
Glass is the important component part of Space Optical System, is mainly used for spacecraft air port glass, reflection or transmission eyeglass, solar-electricity
The protecting cover sheet etc. of Chi Zhen.Space junk is about run with the speed of 10km/s in Low Earth Orbit, constitutes an extremely Pang
Big space environment, existing will cause very big influence to in-orbit spacecraft, satellite etc..Nasa announces space junk
Enormous amount not only threatens in-orbit spacecraft inherently safe, and large-sized fragment also can mutually hit production in flight course
Raw more, smaller minute fragments, and then cause space environment more severe.Fragment below for 1cm at present,
Especially micron order fragment can only take passively safeguard procedures, and therefore, which is industry
Interior research hotspot.A kind of optical glass micron-sized space debris protecting film is provided to be of great immediate significance.
Summary of the invention
The purpose of the present invention is to provide a kind of optical glass micron-sized space debris protecting films, can be used for spacecraft use
The protection of optical glass surface micron-sized space debris has provided to improve the minute fragments defence capability of space optics
Effect means.
To achieve the goals above, present invention employs the following technical solutions:
Optical glass micron-sized space debris protecting film is prepared in optical glass table to be protected by vacuum coating method
On face, including the spring structure, bottom film and nanometer multilayer continuous film being successively set on optical glass surface, spring knot
Structure is combined closely on substrate optical glass, and ingredient is SiO2Or Si3N4;Spring structure is obtained using glancing angle deposition technology,
For buffering the Impact energy of minute fragments;Bottom film is whole continuous film layer, and ingredient is Si or Ti, Si or Ti film layer
It is prepared under argon atmosphere by magnetron sputtering technique;Nano-multilayer film, for whole continuous film layer, ingredient DLC/Al, by
DLC film and Al film multilayer are alternately prepared, and wherein DLC is hard films, and Al is toughening phase, and nano-multilayer film is intended to obtain hardness
Have good film with toughness, reduces fragment and hit the generation for leading to film crack.
Wherein, 0.5 μm~1 μm of spring structure thickness;It is preferred that 0.8 μm~1 μm;
Wherein, DLC film is DLC film, has sp2And sp3The carbon atom spacial framework of electron orbit hydridization;
Further, DLC film passes through C2H2Radio frequency discharge mode obtains under atmosphere, air pressure 5 × 10-2Pa~5 × 10-1Pa,
Radio-frequency power 800W~1000W, thicknesses of layers 20nm~50nm.
Wherein, Al film is prepared under argon atmosphere by magnetron sputtering technique, air pressure 4 × 10-1Pa~1Pa, film thickness
20nm~50nm.
Further, DLC/Al multilayer film includes at least 5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film;It is preferred that 8-10
A modulation unit, i.e. 8-10 layer DLC film, 8-10 layers of Al film;
Wherein, spring structure passes through SiO2Or Si3N4It is prepared under oxygen or nitrogen atmosphere using magnetron sputtering technique,
82 °~88 ° of middle magnetron sputtering particle beams incidence angle, air pressure 4 × 10-1Pa~1Pa.
Further, the transmitance of spring structure visible light wave range is greater than 90%.
Bottom film is used to improve the binding force of spring structure Yu upper part nano-multilayer film, in prepared by magnetron sputtering technique
Air pressure 4 × 10-1Pa~1Pa, 0.2 μm~0.3 μm of film thickness.
Optical glass surface of the present invention is coated with micron-sized space debris protection membrane sample, through speed 6.52km/s
Fragment (diameter 0.5mm, 3 μm of thickness) hit after, without obvious mechanical damage, surface deposits height is not more than 6.650 μ on surface
M, 400nm-800nm wave band mean transmissivity are not less than 79.62%;And optical glass sample is in identical test parameter lower surface
There is substantial radial and annular crack, surface deposits height is 16.547 μm, and 400nm-800nm wave band mean transmissivity is
60.50%, illustrate that protecting film has preferable anti-collision performance.The use of the protecting film is that spacecraft optical glass micron order is empty
Between fragment protective provide powerful measure.
Detailed description of the invention
Fig. 1 is optical glass micron-sized space debris protecting film structure schematic diagram of the invention.
Wherein, 1, nanometer multilayer continuous film;2, bottom film;3, spring structure;
4, non-optical glass substrate.
Specific embodiment
Introduced below is the specific embodiment as content of the present invention, below by specific embodiment to this
The content work of invention further illustrates.Certainly, description following detailed description is only example not Tongfang of the invention
The content in face but should not be understood as the limitation scope of the invention.
Optical glass micron-sized space debris protecting film of the invention, including it is successively set on 4 surface of non-optical glass substrate
On spring structure 3, bottom film 2 and nanometer multilayer continuous film 1.
1 spring structure of embodiment is SiO2, bottom is Si layers
The spring structure that first prepared composition is SiO2 on optical glass, optical glass first carry out cleaning treatment, and ethyl alcohol is molten
Liquid is cleaned by ultrasonic 5min, and is dried.Spring structure is prepared using glancing angle deposition technology, passes through Si under oxygen atmosphere
Target material magnetic sputtering mode prepares SiO2 spring structure, design parameter in optical glass surface are as follows: the magnetron sputtering particle beams is incident
Angle is 82 °, 8 × 10-1Pa of air pressure, magnetron sputtering power 500W, optical glass rotating rate 1.5rpm, time 60min, finally
0.62 μm of thickness of spring structure is obtained, spring structure is combined closely on optical glass face.
Secondly, Si prime coat is prepared on spring structure, by Si target material magnetic sputtering mode in spring under argon atmosphere
The continuous film layer of Si, design parameter are prepared in structure are as follows: 0 °, 4 × 10-1Pa of air pressure of magnetron sputtering particle beams incidence angle, magnetron sputtering
Power 600W, time 30min, the final film layer for obtaining 0.26 μm of thickness.
Finally, preparing nano-multilayer film on Si prime coat, ingredient DLC/Al is alternately made by DLC film and Al film multilayer
Standby to form, DLC/Al multilayer film includes 5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film.The preparation side of 1 unit is set forth below
Method.DLC film layer is prepared first, is obtained by radio frequency discharge mode under C2H2 atmosphere, design parameter are as follows: 8 × 10-2Pa of air pressure is penetrated
Frequency power 800W, time 30s, the thicknesses of layers 22nm of preparation;Secondly pass through Al target magnetic control sputtering technology system under argon atmosphere
Standby Al film, design parameter are as follows: 5 × 10-1Pa of air pressure, radio-frequency power 600W, time 60s, the thicknesses of layers 33nm of preparation.Remaining 4
A unit preparation method above process is identical.
2 spring structure of embodiment is SiO2, bottom is Ti layers
First prepared composition is SiO on optical glass2Spring structure, optical glass first carries out cleaning treatment, and ethyl alcohol is molten
Liquid is cleaned by ultrasonic 5min, and is dried.Spring structure is prepared using glancing angle deposition technology, passes through Si under oxygen atmosphere
Target material magnetic sputtering mode prepares SiO in optical glass surface2Spring structure, design parameter are as follows: the magnetron sputtering particle beams is incident
Angle is 82 °, air pressure 8 × 10-1Pa, magnetron sputtering power 500W, optical glass rotating rate 1.5rpm, time 60min are finally obtained
0.62 μm of thickness of spring structure is obtained, spring structure is combined closely on optical glass face.
Secondly, Ti prime coat is prepared on spring structure, by Ti target material magnetic sputtering mode in spring under argon atmosphere
The continuous film layer of Ti, design parameter are as follows: 0 ° of magnetron sputtering particle beams incidence angle, air pressure 4 × 10 are prepared in structure-1Pa, magnetron sputtering
Power 600W, time 30min, the final film layer for obtaining 0.21 μm of thickness.
Nano-multilayer film is prepared on last Ti prime coat, ingredient DLC/Al is alternately prepared by DLC film and Al film multilayer
It forms, DLC/Al multilayer film includes 5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film.The preparation side of 1 unit is set forth below
Method.DLC film layer is prepared first, passes through C2H2Radio frequency discharge mode obtains under atmosphere, design parameter are as follows: air pressure 8 × 10-2Pa is penetrated
Frequency power 800W, time 30s, the thicknesses of layers 22nm of preparation;Secondly pass through Al target magnetic control sputtering technology system under argon atmosphere
Standby Al film, design parameter are as follows: air pressure 5 × 10-1Pa, radio-frequency power 600W, time 60s, the thicknesses of layers 33nm of preparation.Remaining 4
A unit preparation method above process is identical.
3 spring structure of embodiment is Si3N4, bottom is Si layers
First prepared composition is Si on optical glass layer3N4Spring structure, optical glass first carries out cleaning treatment, ethyl alcohol
Solution is cleaned by ultrasonic 5min, and is dried.Spring structure is prepared using glancing angle deposition technology, is passed through under nitrogen atmosphere
Si target material magnetic sputtering mode prepares Si in optical glass surface3N4Spring structure, design parameter are as follows: the magnetron sputtering particle beams enters
Firing angle is 86 °, air pressure 6 × 10-1Pa, magnetron sputtering power 500W, optical glass rotating rate 1.5rpm, time 60min, finally
0.54 μm of thickness of spring structure is obtained, spring structure is combined closely on optical glass face.
Secondly, Si prime coat is prepared on spring structure, by Si target material magnetic sputtering mode in spring under argon atmosphere
The continuous film layer of Si, design parameter are as follows: 0 ° of magnetron sputtering particle beams incidence angle, air pressure 4 × 10 are prepared in structure-1Pa, magnetron sputtering
Power 600W, time 30min, the final film layer for obtaining 0.26 μm of thickness.
Nano-multilayer film is prepared on last Si prime coat, ingredient DLC/Al is alternately prepared by DLC film and Al film multilayer
It forms, DLC/Al multilayer film includes 5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film.The preparation side of 1 unit is set forth below
Method.DLC film layer is prepared first, passes through C2H2Radio frequency discharge mode obtains under atmosphere, design parameter are as follows: air pressure 8 × 10-2Pa is penetrated
Frequency power 800W, time 30s, the thicknesses of layers 22nm of preparation;Secondly pass through Al target magnetic control sputtering technology system under argon atmosphere
Standby Al film, design parameter are as follows: air pressure 5 × 10-1Pa, radio-frequency power 600W, time 60s, the thicknesses of layers 33nm of preparation.Remaining 4
A unit preparation method above process is identical.
4 spring structure of embodiment is Si3N4, bottom is Ti layers
First prepared composition is Si on optical glass layer3N4Spring structure, optical glass first carries out cleaning treatment, ethyl alcohol
Solution is cleaned by ultrasonic 5min, and is dried.Spring structure is prepared using glancing angle deposition technology, is passed through under nitrogen atmosphere
Si target material magnetic sputtering mode prepares Si in optical glass surface3N4Spring structure, design parameter are as follows: the magnetron sputtering particle beams enters
Firing angle is 86 °, air pressure 6 × 10-1Pa, magnetron sputtering power 500W, optical glass rotating rate 1.5rpm, time 60min, finally
0.54 μm of thickness of spring structure is obtained, spring structure is combined closely on optical glass face.
Secondly, Ti prime coat is prepared on spring structure, by Ti target material magnetic sputtering mode in spring under argon atmosphere
The continuous film layer of Ti, design parameter are as follows: 0 ° of magnetron sputtering particle beams incidence angle, air pressure 4 × 10 are prepared in structure-1Pa, magnetron sputtering
Power 600W, time 30min, the final film layer for obtaining 0.21 μm of thickness.
Nano-multilayer film is prepared on last Si prime coat, ingredient DLC/Al is alternately prepared by DLC film and Al film multilayer
It forms, DLC/Al multilayer film includes 5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film.The preparation side of 1 unit is set forth below
Method.DLC film layer is prepared first, passes through C2H2Radio frequency discharge mode obtains under atmosphere, design parameter are as follows: air pressure 8 × 10-2Pa is penetrated
Frequency power 800W, time 30s, the thicknesses of layers 22nm of preparation;Secondly pass through Al target magnetic control sputtering technology system under argon atmosphere
Standby Al film, design parameter are as follows: air pressure 5 × 10-1Pa, radio-frequency power 600W, time 60s, the thicknesses of layers 33nm of preparation.Remaining 4
A unit preparation method above process is identical.
Following list illustrates that different embodiments obtain the performance of protecting film.
Fragment hits rear protecting film properties comparison (speed: 6.52km/s, diameter: 0.5mm, thickness: 3 μm)
Although the detailed description and description of the specific embodiments of the present invention are given above, it should be noted that
Those skilled in the art can spirit according to the present invention various equivalent changes and modification, institute are carried out to above embodiment
The function of generation, should all be within that scope of the present invention in the spirit covered without departing from specification and attached drawing.
Claims (9)
1. optical glass micron-sized space debris protecting film, optical glass surface to be protected is prepared in by vacuum coating method
On, including the spring structure, bottom film and nanometer multilayer continuous film being successively set on optical glass surface, spring structure
It combines closely on substrate optical glass, and ingredient is SiO2Or Si3N4;Spring structure is obtained using glancing angle deposition technology, is used
In the Impact energy of buffering minute fragments;Bottom film is whole continuous film layer, and ingredient is Si or Ti, Si or Ti film layer
It is prepared under argon atmosphere by magnetron sputtering technique;Nano-multilayer film, for whole continuous film layer, ingredient DLC/Al, by
DLC film and Al film multilayer are alternately prepared, and wherein DLC is hard films, and Al is toughening phase, and nano-multilayer film is intended to obtain hardness
The all good film with toughness reduces fragment and hits the generation for leading to film crack.
2. optical glass micron-sized space debris protecting film as described in claim 1, wherein spring structure thickness 0.5 μm~1
μm。
3. optical glass micron-sized space debris protecting film as described in claim 1, wherein DLC film is DLC film,
With sp2And sp3The carbon atom spacial framework of electron orbit hydridization.
4. optical glass micron-sized space debris protecting film as claimed in claim 3, wherein DLC film passes through C2H2It is penetrated under atmosphere
Frequency discharge mode obtains, air pressure 5 × 10-2Pa~5 × 10-1Pa, radio-frequency power 800W~1000W, thicknesses of layers 20nm~
50nm。
5. optical glass micron-sized space debris protecting film as described in claim 1, wherein Al film passes through under argon atmosphere
Magnetron sputtering technique preparation, air pressure 4 × 10-1Pa~1Pa, film thickness 20nm~50nm.
6. optical glass micron-sized space debris protecting film as described in claim 1, wherein DLC/Al multilayer film includes at least
5 modulation units, i.e. 5 layers of DLC film, 5 layers of Al film.
7. optical glass micron-sized space debris protecting film as described in claim 1, wherein spring structure passes through SiO2Or
Si3N4It is prepared under oxygen or nitrogen atmosphere using magnetron sputtering technique, wherein 82 °~88 ° of magnetron sputtering particle beams incidence angle,
Air pressure 4 × 10-1Pa~1Pa.
8. optical glass micron-sized space debris protecting film as described in claim 1, wherein the visible light wave range of spring structure
Transmitance be greater than 90%.
9. optical glass micron-sized space debris protecting film as described in claim 1, wherein bottom film is for improving spring
The binding force of structure and upper part nano-multilayer film, magnetron sputtering technique preparation in air pressure 4 × 10-1Pa~1Pa, film thickness
0.2 μm~0.3 μm.
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CN101602273A (en) * | 2009-07-22 | 2009-12-16 | 天津南玻节能玻璃有限公司 | A kind of diamond-like carbon film-coating glass and preparation method thereof |
CN101665904A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Aluminum-containing diamond-like carbon film and method for preparing same |
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US7445273B2 (en) * | 2003-12-15 | 2008-11-04 | Guardian Industries Corp. | Scratch resistant coated glass article resistant fluoride-based etchant(s) |
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CN101665904A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Aluminum-containing diamond-like carbon film and method for preparing same |
CN101602273A (en) * | 2009-07-22 | 2009-12-16 | 天津南玻节能玻璃有限公司 | A kind of diamond-like carbon film-coating glass and preparation method thereof |
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