CN102941712A - Polymer material-metal oxide film composite material and preparation method thereof - Google Patents
Polymer material-metal oxide film composite material and preparation method thereof Download PDFInfo
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- CN102941712A CN102941712A CN2012104057052A CN201210405705A CN102941712A CN 102941712 A CN102941712 A CN 102941712A CN 2012104057052 A CN2012104057052 A CN 2012104057052A CN 201210405705 A CN201210405705 A CN 201210405705A CN 102941712 A CN102941712 A CN 102941712A
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000642 polymer Polymers 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 69
- 230000007704 transition Effects 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 239000013077 target material Substances 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 230000008859 change Effects 0.000 claims description 13
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 229920005570 flexible polymer Polymers 0.000 abstract 2
- 229920000307 polymer substrate Polymers 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 74
- 239000000835 fiber Substances 0.000 description 24
- 239000010936 titanium Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- -1 polypropylene Polymers 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 238000007562 laser obscuration time method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
The invention discloses a polymer material-metal oxide film composite material and a preparation method thereof. The polymer material-metal oxide film composite material is prepared by the following steps of employing high-purity transition metal as a target material and the polymer material as a substrate, firstly preparing a transition layer changing from a pure metal to a metal oxide with low valence and to a metal oxide with high valence on the polymer substrate; and then preparing the metal oxide film layer. The pure metal between the transition layer and the substrate junction surface has good flexibility and strong malleability, matches with the physical properties of a flexible polymer substrate; lowers film inner stress caused by mismatching materials, can prevent cracks in the film from extension along the junction layer, allowing the binding strength between the flexible polymer material and the metal oxide film to be increased significantly.
Description
Technical field
The present invention relates to a kind of macromolecular material-metal-oxide film composite and preparation method thereof, belong to film base composite functional polymeric material field.
Background technology
Transition group metallic oxide has abundant valence state and valence shell configuration, and chemical reaction and crystal structure types are abundant, and the character of a lot of excellences is arranged at aspects such as superconduction, giant magnetoresistance, dielectrics.The transition group nano-metal-oxide mainly is as matrix take various macromolecular materials in the application aspect the flexible high molecular material functional modification, through blend, the technology such as surface deposition with nano-metal-oxide with molecule, powder or filminess, undertaken compound by direct or indirect mode and flexible macromolecule base material, make flexible high molecular material can not only keep original style, such as flexibility, stretching property by force, corrosion-resistant, the characteristics such as air-tightness is good, and have some specific functions of transition group nano-metal-oxide, such as antistatic behaviour, automatically cleaning, antibiotic, ultraviolet ray and infrared ray had the performances such as reflection and absorption, in catalysis, sensing, optics, the field such as magnetics and battery is with a wide range of applications.
The existing transition group nano-metal-oxide that adopts carries out modification as filler to flexible high molecular material both at home and abroad at present, and preparation has the flexible high molecular material of photo-catalysis function.But all exist the dispersion of nano particle and nano particle in the process of using transition group nano-metal-oxide particle that macromolecular material is processed to the problem that affects of flexible high molecular material subjectivity property.To adopt nano particle as the scattering problem of filler in order overcoming, to be applied in the study on the modification of film base composite high-molecular material based on the liquid phase method of surface film deposition technique, chemical vapour deposition technique, physical vaporous deposition etc.But because flexible high molecular material is different from the physical and chemical performance of inorganic, metal oxide, film growth belongs to heteroepitaxial growth, matching between the film base is bad,, lattice constant mismatch excessive such as elastic modelling quantity and difference of thermal expansion coefficients etc., film base interface very easily produces stress and concentrates, therefore the interface around the multiple district of composite inner damage and defective often, directly affected the functional reliability of composite functional material.
The method of change film base interface bonding state commonly used is that macromolecular material is carried out the surface plasma preliminary treatment the most at present.Patent " plastic-thin metal film and manufacture method thereof " (WO2008/054173), pass through plasma treatment, produce reactive effect base on the plastic basis material surface, and contain the adhesive composition that can carry out with described reactive effect base chemically combined reactive materials in the coating of described plastic basis material, and described plastic basis material and metallic film is bonding, thereby the bond strength between raising plastic basis material and metallic film.Plasma treatment can be improved surface of polymer material activity and surface energy effectively, increases it to the affinity of inorganic thin film, improves the binding strength of film based composites with this.But cold plasma pretreatment technique is complicated, and has the problem of the base material loss in weight after plasma treatment, will affect the mechanical performance of composite functional material.
Summary of the invention
The purpose of this invention is to provide a kind of macromolecular material-metal-oxide film composite and preparation method thereof.
Macromolecular material of the present invention-metal-oxide film composite, comprise macromolecular material base material and transition group metallic oxide film, between base material and the film transition zone is arranged, transition zone is followed successively by simple metal, the paramount valent metal oxide of low price gradual change from base material toward the film direction, until identical with metal-oxide film.The middle transition layer thickness is decided according to magnesium-yttrium-transition metal material and required preparation metal-oxide film thickness, is generally 1/20 to 1/3 of film thickness.The price of metallic atom in described metal suboxide and the high-valency metal oxide all is not higher than the price (lower with) of metallic atom in the described metal-oxide film.
Macromolecular material of the present invention-metal-oxide film composite manufacture method is: take high-purity magnesium-yttrium-transition metal as target, macromolecular material is base material, adopt magnetron sputtering technique, preferred magnetically controlled DC sputtering technology, at first prepare by simple metal to metal suboxide at polymer base material, gradual change prepares the metal-oxide film layer again to the transition zone of high price oxide again.
The transition zone preparation method is: after sputter begins, open the oxygen flow valve, pass into oxygen, within a certain period of time oxygen flow is transferred to the setting flow gradually.
After setting flow, keep oxygen flow constant, sputter obtains the metal-oxide film layer.
Under the no oxygen flow condition, the substrate surface deposit is simple metal; Under low oxygen flow condition, the substrate surface deposit is metal suboxide; Increase gradually with oxygen flow, the substrate surface deposit is from the paramount valent metal oxide of metal suboxide gradual change; To setting value, then form metal-oxide film, between base material and metal-oxide film, prepared like this by simple metal to metal suboxide, again the film base interface transition layer of the paramount valent metal oxide of gradual change.
The setting flow of above-mentioned oxygen is take the flow value that can form the thin layer metal oxide as lower limit, take the flow value of oxidized metal target not as the upper limit, the time of transition zone sputter decides according to magnesium-yttrium-transition metal material and required preparation metal-oxide film thickness, the preparation time of metal-oxide film layer is definite by conventional method according to its thickness, and other splash-proofing sputtering process parameters are determined by conventional method.
Further, before sputter began, base material preferably carried out preliminary treatment, as by methods such as cleanings, and with the organic solvent of removal material surface, the impurity such as dust, then oven dry; In addition, also can carry out first pre-sputter, to remove the oxide of target material surface, to reach better effect.
Owing to having adopted technique scheme, the present invention to have following advantage and effect:
Method of the present invention has been by having prepared between flexible macromolecule base material and metal-oxide film by simple metal to metal suboxide, again the film base interface transition layer of the paramount valent metal oxide of gradual change.The buffer layer material modulus needs to have dwindled modulus difference between metal-oxide film and the synthetic fibers base material between thin-film material and base material modulus.Flexible with the simple metal of base material faying face in the transition zone, the row that extends is strong, be complementary with the physical property of flexible macromolecule base material, reduced since material do not mate the stress in thin films that causes, and can expand along between binder course by the block film internal fissure, the binding strength of flexible high molecular material and metal-oxide film is significantly improved.
Method of the present invention is simple, and one step of operation finishes, and has certain environmental protection effect.
Description of drawings
Fig. 1 is that different transition zone coated fibers are at the SEM photo of deciding under the elongation condition;
Fig. 2 is the film basic mode amount schematic diagram of optimizing integration;
Fig. 3 is for arranging metal Ti transition zone plated film composite fibre modulus change schematic diagram.
The specific embodiment
Below in conjunction with the surface deposition nano-TiO
2Film polypropylene fiber and preparation method thereof is described further the present invention, but is not construed as limiting the invention.
In order to dwindle TiO
2Modulus difference between film and the synthetic fibers base material, the stress at m flac base interface, the buffer layer material modulus needs between thin-film material and base material modulus, and with film and base material preferably adhesion property is arranged.Effect that it is generally acknowledged the transition zone that has simultaneously composition and structure gradual change characteristics concurrently is best.
TiO
2It is the highest price oxide of metal Ti, under the identical condition of sputter basic parameter, the sputter rate of common metal is more much higher than the sputter rate of its corresponding oxide, the deposited particles energy is high, be higher than its sull with the flexible parent metal adhesion, and deposited particles is strong in the fiber surface diffusivity, the deposit film mesopore is less, the film relative density is high, and compactness is good.Simultaneously, the Ti metal has higher toughness and cold draw than oxide.Therefore experiment is take Ti metal and low oxide thereof as transition zone, at polypropylene fiber surface deposition nano-TiO
2Film has designed following experimental program, and the research interface transition layer is on the impact of plated film sample mechanical performance, film base interfacial combined function and plated film composite high-molecular material reliability.
Concrete steps are as follows:
(1) base material preliminary treatment: polypropylene fiber is washed 30 min with ultrasonic washer in acetone soln, with the organic solvent of removal material surface, the impurity such as dust, the baking oven of then putting into 40-45 ℃ is dried;
(2) pre-sputter: install target and base material at magnetron sputtering apparatus, reative cell is evacuated to base vacuum 1.5 * 10
-4Then Pa passes into high-purity argon gas (99.999 %) as sputter gas, sputtering power 50 W, and 0.5 Pa, argon flow amount 40 ml/min are pressed in work, and pre-sputter 5 min are to remove the oxide on target surface.
(3) keep the sputtering technology condition of polypropylene fiber constant, according to following 3 schemes at polypropylene fiber (7.69 dtex) surface deposition nano-TiO
2Film:
Scheme one: after sputter begins, directly open the oxygen flow valve, control oxygen flow 10 ml/min, sputtering time 60 min, the titanium atom that sputters is combined with the oxygen crash response, directly forms TiO on the polypropylene fiber surface
2Film.
Scheme two: after sputter begins 10 min, open the oxygen flow valve, the control oxygen flow is 10 ml/min, again sputter 50 min.Obstructed oxygen in 10 min had formed the grey metal Ti film with metallic luster at primary colors polypropylene fiber substrate surface after sputter began, and opened subsequently the oxygen flow valve, the control oxygen flow is 10 ml/min, sputter 50 min again, it is white that the film color turns gradually, forms TiO
2Film, this scheme is at polypropylene fiber base material and TiO
2Be provided with the metal Ti transition zone between the film.
Scheme three: after sputter begins, open the oxygen flow valve, in 10 min, slowly oxygen flow is transferred to 10 ml/min, again sputter 50 min.After sputter begins, under obstructed oxygen and low oxygen flow condition, deposited darker metal Ti and the low price Ti oxide of color at the polypropylene fibre substrate surface, when oxygen flow increases to 10 ml/min, the titanium atom that sputters is combined fully with the oxygen crash response, form the titanium dioxide of white, again sputter 50 min.This scheme is at polypropylene fiber base material and TiO
2Be provided with between the film by the Ti metal to Ti oxide at a low price, gradual change is to high price Ti oxide interface transition zone again.
By scheme one, two, three at the polypropylene fiber surface deposition nano-TiO
2Film, the SEM photo of plated film composite fibre axial tension 3 % as shown in Figure 1, (a) plated film composite fibre without transition zone, Direct precipitation of obtaining for employing scheme one wherein; (b) the plated film composite fibre that the metal Ti transition zone is arranged that employing scheme two obtains; (c) the Ti metal that obtains of employing scheme three is to Ti oxide at a low price, to the plated film composite fibre of high price Ti oxide transition zone.
Comparison diagram 1 (a), (b) and (c), in the situation that longitudinal stretch ratio is 3%, have clear improvement by the experimental program one prepared transition zone coated fibers that do not add by experimental program two prepared plated film composite fibre face crack density, and almost do not have crackle to occur by experimental program three prepared plated film composite fibre surfaces.Illustrate and press three depositing nano TiO of experimental program
2Film quality and film base interfacial combined function are good, and the reliability of plated film composite is high.
By the surface deposition nano-TiO
2Polypropylene fiber axial rift test experiments result as can be known, the plated film composite fibre that Ti oxide gradational contact transition zone at a low price is set is good than Direct precipitation and the plated film composite fibre film base binding performance take Ti as interface transition layer, the composite reliability is high.Analyzing its reason, mainly is the coupling of buffer layer material performance.Fig. 2 is the film basic mode amount schematic diagram of optimizing integration, and as can be seen from the figure, the modulus change between film and the base material has the stage of a transition, and the relaxed stress at film base interface of this layer transition zone has improved both combinations.Although dwindled modulus difference between base material and the film by experimental program two set intermediate layers, but and base material and and film between do not occur as modulus transition region shown in Figure 2, increase on the contrary the interface of a combination, as shown in Figure 3, increased the probability that has defective.But and by experimental program three set transition zones be metal material with relaxed stress as bottom, then be transitioned into gradually last TiO
2Coating makes transition zone have simultaneously composition and structure gradual change characteristics concurrently, thus alleviated since material do not mate the internal stress that causes, and can expand along interlayer by the block film internal fissure, thereby the adhesive force of enhanced film makes the surface deposition nano-TiO
2The reliability of textile material is improved.
The present invention is applied to other metal-oxide film composite manufacture, such as ZnO, Fe
2O
3, SnO
2Deng, can realize similar technique effect.
Claims (6)
1. macromolecular material-metal-oxide film composite, comprise macromolecular material base material and transition group metallic oxide film, it is characterized in that: between described base material and the described metal-oxide film transition zone is arranged, described transition zone is followed successively by simple metal, the paramount valent metal oxide of low price gradual change from described base material toward described film direction, until identical with metal-oxide film.
2. macromolecular material as claimed in claim 1-metal-oxide film composite, it is characterized in that: the thickness of described transition zone is 1/20 to 1/3 of described metal-oxide film thickness.
3. method for preparing macromolecular material as claimed in claim 1 or 2-metal-oxide film composite, adopt magnetron sputtering technique, take high-purity magnesium-yttrium-transition metal as target, macromolecular material is base material, it is characterized in that: at first in the preparation of described base material by simple metal to metal suboxide, gradual change is to the transition zone of high price oxide again, prepare again the metal-oxide film layer, the preparation method of described transition zone is, after sputter begins, open the oxygen flow valve, regulate gradually oxygen flow to setting flow.
4. method as claimed in claim 3, it is characterized in that: described magnetron sputtering technique is the magnetically controlled DC sputtering technology.
5. such as claim 3 or 4 described methods, it is characterized in that: before sputter begins, described base material is cleaned, then oven dry.
6. such as claim 3 or 4 described methods, it is characterized in that: before sputter begins, carry out first pre-sputter, to remove the oxide of described target material surface.
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| CN201210405705.2A CN102941712B (en) | 2012-10-23 | 2012-10-23 | Polymer material-metal oxide film composite material and preparation method thereof |
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| CN201210405705.2A CN102941712B (en) | 2012-10-23 | 2012-10-23 | Polymer material-metal oxide film composite material and preparation method thereof |
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| CN102941712B CN102941712B (en) | 2015-07-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105817270A (en) * | 2016-05-18 | 2016-08-03 | 中国科学院山西煤炭化学研究所 | Preparation method of metal-oxide dual-interface catalyst |
| CN105873371A (en) * | 2015-11-06 | 2016-08-17 | 武汉光谷创元电子有限公司 | Substrate and manufacture method thereof |
| CN105903480A (en) * | 2016-05-18 | 2016-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of double-interface catalyst for one-process hydrogen production-hydrogenation coupling reaction and application of catalyst |
| CN108106748A (en) * | 2017-11-09 | 2018-06-01 | 中国电子科技集团公司第四十八研究所 | A kind of flexibility ablation resistance film and preparation method thereof |
| CN111655490A (en) * | 2017-12-28 | 2020-09-11 | 网络技术服务株式会社 | Substrate bonding method, transparent substrate laminate, and device provided with substrate laminate |
| CN113667936A (en) * | 2021-09-06 | 2021-11-19 | 湖北中烟工业有限责任公司 | High-temperature oxidation-resistant ultrathin heating film and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017083166A1 (en) * | 2015-11-13 | 2017-05-18 | 3M Innovative Properties Company | Anti-microbial articles and methods of using same |
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|---|---|---|---|---|
| US4462883A (en) * | 1982-09-21 | 1984-07-31 | Pilkington Brothers P.L.C. | Low emissivity coatings on transparent substrates |
| CN1851038A (en) * | 2006-05-25 | 2006-10-25 | 北京科技大学 | Method for preparing chromium oxide composite coating |
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2012
- 2012-10-23 CN CN201210405705.2A patent/CN102941712B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4462883A (en) * | 1982-09-21 | 1984-07-31 | Pilkington Brothers P.L.C. | Low emissivity coatings on transparent substrates |
| CN1851038A (en) * | 2006-05-25 | 2006-10-25 | 北京科技大学 | Method for preparing chromium oxide composite coating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105873371A (en) * | 2015-11-06 | 2016-08-17 | 武汉光谷创元电子有限公司 | Substrate and manufacture method thereof |
| CN105873371B (en) * | 2015-11-06 | 2019-11-01 | 武汉光谷创元电子有限公司 | Substrate and its manufacturing method |
| CN105817270A (en) * | 2016-05-18 | 2016-08-03 | 中国科学院山西煤炭化学研究所 | Preparation method of metal-oxide dual-interface catalyst |
| CN105903480A (en) * | 2016-05-18 | 2016-08-31 | 中国科学院山西煤炭化学研究所 | Preparation method of double-interface catalyst for one-process hydrogen production-hydrogenation coupling reaction and application of catalyst |
| CN108106748A (en) * | 2017-11-09 | 2018-06-01 | 中国电子科技集团公司第四十八研究所 | A kind of flexibility ablation resistance film and preparation method thereof |
| CN111655490A (en) * | 2017-12-28 | 2020-09-11 | 网络技术服务株式会社 | Substrate bonding method, transparent substrate laminate, and device provided with substrate laminate |
| CN111655490B (en) * | 2017-12-28 | 2023-06-02 | 网络技术服务株式会社 | Method for bonding substrates, substrate laminate, and device provided with substrate laminate |
| CN113667936A (en) * | 2021-09-06 | 2021-11-19 | 湖北中烟工业有限责任公司 | High-temperature oxidation-resistant ultrathin heating film and preparation method thereof |
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| CN102941712B (en) | 2015-07-22 |
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