CN102941712B - 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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- CN102941712B CN102941712B CN201210405705.2A CN201210405705A CN102941712B CN 102941712 B CN102941712 B CN 102941712B CN 201210405705 A CN201210405705 A CN 201210405705A CN 102941712 B CN102941712 B CN 102941712B
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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 12
- 229920000642 polymer Polymers 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 66
- 230000007704 transition Effects 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 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
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 230000008859 change Effects 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims 1
- 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 16
- 239000004743 Polypropylene Substances 0.000 description 12
- -1 polypropylene Polymers 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 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 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000002105 nanoparticle 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
- 239000007769 metal material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 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
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- 239000011230 binding agent Substances 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
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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 Polymer material-metal oxide film composite material 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 enrich, and has a lot of excellent character in superconduction, giant magnetoresistance, dielectric etc.The application of transition group nano-metal-oxide in flexible high molecular material functional modification mainly with various macromolecular material for matrix, through blended, the technology such as surface deposition by nano-metal-oxide with molecule, powder or filminess, compound is carried out by direct or indirect mode and flexible macromolecule base material, make the style that flexible high molecular material can not only keep original, as flexibility, stretching property by force, corrosion-resistant, the characteristics such as air-tightness is good, and there are some specific functions of transition group nano-metal-oxide, as antistatic behaviour, automatically cleaning, antibacterial, ultraviolet and infrared ray are had to 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 there is the dispersion of nano particle and nano particle in the process using transition group metal oxide nano particles to process macromolecular material and problem is affected on flexible high molecular material subjectivity property.In order to overcome the scattering problem adopting nano particle as filler, liquid phase method, chemical vapour deposition technique, physical vaporous deposition etc. based on surface film deposition technique are applied in the study on the modification of film base composite high-molecular material.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 film base is bad, as elastic modelling quantity with difference of thermal expansion coefficients is excessive, lattice constant mismatch etc., film base interface very easily produces stress and concentrates, therefore composite inner damage and the multiple district of defect often of the surrounding at interface, directly affects the functional reliability of composite functional material.
The method of change film base interface fine structure the most conventional at present carries out surface plasma pretreatment to macromolecular material.Patent " plastic-thin metal film and manufacture method thereof " (WO2008/054173), pass through plasma treatment, reactive effect base is produced on the surface at plastic basis material, and coating contains the adhesive composition that can carry out chemically combined reactive materials with described reactivity effect base on described plastic basis material, and by described plastic basis material and metallic film bonding, thus improve the bond strength between plastic basis material and metallic film.Plasma treatment can improve the active and surface energy of surface of polymer material effectively, increases its affinity to inorganic thin film, improves the binding strength of film based composites with this.But cold plasma pretreatment technique is more complicated, and after plasma treatment, there is the problem of substrate weight loss, will the mechanical performance of composite functional material be affected.
Summary of the invention
The object of this invention is to provide a kind of Polymer material-metal oxide film composite material and preparation method thereof.
Polymer material-metal oxide film composite material of the present invention, comprise macromolecular material base material and transition group metallic oxide film, transition zone is had between base material and film, transition zone is followed successively by simple metal, at a low price gradual change to higher valence metal oxide toward film direction, until identical with metal-oxide film from base material.Middle transition layer thickness according to magnesium-yttrium-transition metal material and needed for prepare metal-oxide film thickness and determine, be generally 1/20 to 1/3 of film thickness.The price of metallic atom in described metal suboxide and higher valence metal oxide, all not higher than the price (lower with) of metallic atom in described metal-oxide film.
The preparation method of Polymer material-metal oxide film composite material of the present invention is: with high-purity magnesium-yttrium-transition metal for target, macromolecular material is base material, adopt magnetron sputtering technique, preferred magnetically controlled DC sputtering technology, first prepare by simple metal to metal suboxide on polymer base material, gradual change is to the transition zone of high oxide again, then prepares metallic oxide film.
Transition zone preparation method is: after sputtering starts, open oxygen flow valve, pass into oxygen, within a certain period of time oxygen flow is adjusted to setting flow gradually.
To setting flow, keep oxygen flow constant, sputtering obtains metallic oxide film.
Under no oxygen flow condition, substrate surface deposit is simple metal; Under low oxygen flow condition, substrate surface deposit is metal suboxide; Increase gradually with oxygen flow, substrate surface deposit is from metal suboxide gradual change to higher valence metal oxide; To setting value, then form metal-oxide film, prepared by simple metal to metal suboxide between base material and metal-oxide film like this, then gradual change is to the film base interface transition layer of higher valence metal oxide.
Above-mentioned oxygen set flow so that the flow value of thin layer metal oxide can be formed as lower limit, with the flow value of not oxidized metal target for the upper limit, time of transition zone sputtering according to magnesium-yttrium-transition metal material and needed for prepare metal-oxide film thickness and determine, the preparation time of metallic oxide film is determined by conventional method according to its thickness, and other splash-proofing sputtering process parameters are determined by conventional method.
Further, before sputtering starts, base material preferably carries out pretreatment, and as passed through the methods such as cleaning, to remove the organic solvent of material surface, the impurity such as dust, then dry; In addition, also first pre-sputtering can be carried out, to remove the oxide of target material surface, to reach better effect.
Owing to have employed technique scheme, tool of the present invention has the following advantages and effect:
Method of the present invention by having prepared by simple metal to metal suboxide between flexible macromolecule base material and metal-oxide film, then gradual change is to the film base interface transition layer of higher valence metal oxide.Buffer layer material modulus between thin-film material and base material modulus, need reduce modulus difference between metal-oxide film and synthetic fibers base material.Flexible with the simple metal of base material faying face in transition zone, the row that extends is strong, match with the physical property of flexible macromolecule base material, reduce and do not mate due to material the stress in thin films caused, and can expand along between binder course by 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 operation one step completes, and has certain environmental protection effect.
Accompanying drawing explanation
Fig. 1 is that different transition zone coated fibers is determining the SEM photo under elongation condition;
Fig. 2 is that film basic mode amount is optimized integration schematic diagram;
Fig. 3 is for arranging metal Ti transition zone plated film composite fibre modulus change schematic diagram.
Detailed description of the invention
Below in conjunction with 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 reduce TiO
2modulus difference between film and synthetic fibers base material, the stress at m flac base interface, buffer layer material modulus between thin-film material and base material modulus, and need have good adhesion property with film and base material.It is generally acknowledged that the effect of the transition zone simultaneously having composition and structure gradual change feature concurrently is best.
TiO
2it is the highest price oxide of metal Ti, under the condition that sputtering basic parameter is identical, the sputter rate of the sputter rate oxide more corresponding than it of common metal is much higher, deposited particles energy is high, with flexible parent metal adhesion higher than its sull, and deposited particles is strong in fiber surface diffusivity, and deposit film mesopore is less, film relative density is high, and compactness is good.Meanwhile, Ti metal has higher toughness and metal ductility than oxide.Therefore test with Ti metal and low oxide thereof for transition zone, at polypropylene fiber surface deposition nano-TiO
2film, devises following experimental program, and 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 pretreatment: polypropylene fiber is washed 30 min with ultrasonic washer in acetone soln, to remove the organic solvent of material surface, the impurity such as dust, the baking oven then putting into 40-45 DEG C is dried;
(2) pre-sputtering: install target and base material on magnetron sputtering apparatus, is evacuated to base vacuum 1.5 × 10 by reative cell
-4pa, then passes into high-purity argon gas (99.999 %) as sputter gas, sputtering power 50 W, and work pressure 0.5 Pa, argon flow amount 40 ml/min, pre-sputtering 5 min, 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 sputtering starts, directly open oxygen flow valve, control oxygen flow 10 ml/min, sputtering time 60 min, the titanium atom sputtered is combined with oxygen crash response, directly forms TiO on polypropylene fiber surface
2film.
Scheme two: after sputtering beginning 10 min, open oxygen flow valve, controlling oxygen flow is 10 ml/min, then sputters 50 min.After sputtering starts, obstructed oxygen in 10 min, defines the grey metal Ti film with metallic luster, opens oxygen flow valve subsequently at primary colors polypropylene fiber substrate surface, controlling oxygen flow is 10 ml/min, sputter 50 min again, film color turns white gradually, forms TiO
2film, this scheme is at polypropylene fiber base material and TiO
2metal Ti transition zone is provided with between film.
Scheme three: after sputtering starts, open oxygen flow valve, slowly oxygen flow is adjusted to 10 ml/min, then sputter 50 min in 10 min.After sputtering starts, under obstructed oxygen and low oxygen flow condition, the darker metal Ti of color and low price Ti oxide is deposited at polypropylene fibre substrate surface, when oxygen flow is increased to 10 ml/min, the titanium atom sputtered is combined fully with oxygen crash response, form the titanium dioxide of white, then sputter 50 min.This scheme is at polypropylene fiber base material and TiO
2be provided with between film by Ti metal to low price Ti oxide, then gradual change is to high price Ti oxide interface transition zone.
By scheme one, two, three at polypropylene fiber surface deposition nano-TiO
2film, the SEM photo of plated film composite fibre axial tension 3 % as shown in Figure 1, wherein (a) plated film composite fibre without transition zone, Direct precipitation of obtaining for employing scheme one; The plated film composite fibre of what b () employing scheme two obtained have metal Ti transition zone; C Ti metal that () employing scheme three obtains is to low price Ti oxide, extremely at high price the plated film composite fibre of Ti oxide transition zone.
Comparison diagram 1 (a), (b) and (c), when longitudinal stretch ratio is 3%, the do not add transition zone coated fibers of plated film composite fiber surface crack density empirically prepared by scheme two more empirically prepared by scheme one has clear improvement, and the plated film composite fiber surface empirically prepared by scheme three does not almost have crackle to occur.Empirically scheme three depositing nano TiO are described
2film quality and film base interfacial combined function good, the reliability of plated film composite is high.
By surface deposition nano-TiO
2polypropylene fiber axial rift test experiments result is known, and the plated film composite fibre arranging at a low price Ti oxide gradational contact transition zone is compared with Direct precipitation and be that the plated film composite fibre film base binding performance of interface transition layer is good with Ti, and composite reliability is high.Analyze its reason, mainly the coupling of buffer layer material performance.Fig. 2 is that film basic mode amount is optimized integration schematic diagram, and as can be seen from the figure, the modulus change between film and base material has the stage of a transition, and this layer of transition zone relaxes the stress at film base interface, improves both combinations.Although the intermediate layer empirically set by scheme two reduces the modulus difference between base material and film, but and base material and and film between there is not shown in Fig. 2 modulus transition region, add an interface combined on the contrary, as shown in Figure 3, add the probability of existing defects.And the transition zone empirically set by scheme three be using can the metal material of relaxed stress as bottom, be then transitioned into last TiO gradually
2coating, makes transition zone have composition and structure gradual change feature concurrently simultaneously, thus alleviates not mate due to material the internal stress caused, and can expand along interlayer by block film internal fissure, thus the adhesive force of enhanced film, make surface deposition nano-TiO
2the reliability of textile material is improved.
The present invention is applied to the preparation of other metal oxide film composite material, as ZnO, Fe
2o
3, SnO
2deng, similar technique effect can be realized.
Claims (6)
1. macromolecular material-metal oxide film composite material, comprises macromolecular material base material and transition group metallic oxide film, it is characterized in that: described macromolecular material base material is synthetic fibers base material; Have transition zone between described base material and described metal-oxide film, described transition zone is followed successively by simple metal, at a low price gradual change to higher valence metal oxide toward described film direction, until identical with metal-oxide film from described base material.
2. macromolecular material-the metal oxide film composite material as described in claim 1, is characterized in that: the thickness of described transition zone is 1/20 to 1/3 of described metal-oxide film thickness.
3. prepare the method for the macromolecular material-metal oxide film composite material as described in claim 1 or 2 for one kind, adopt magnetron sputtering technique, with high-purity magnesium-yttrium-transition metal for target, macromolecular material is base material, it is characterized in that: prepare first on the substrate by simple metal to metal suboxide, again gradual change to the transition zone of high oxide, prepare metallic oxide film again, the preparation method of described transition zone is, after sputtering starts, opening oxygen flow valve, regulating oxygen flow to setting flow gradually.
4. the method as described in claim 3, is characterized in that: described magnetron sputtering technique is magnetically controlled DC sputtering technology.
5. the method as described in claim 3 or 4, is characterized in that: before sputtering starts, clean, then dry described base material.
6. the method as described in claim 3 or 4, is characterized in that: before sputtering starts, first carry out pre-sputtering, to remove the oxide of described target material surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108430524A (en) * | 2015-11-13 | 2018-08-21 | 3M创新有限公司 | Antimicrobial articles and its application method |
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|---|---|---|---|---|
| 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 |
| CN108106748B (en) * | 2017-11-09 | 2020-12-11 | 中国电子科技集团公司第四十八研究所 | Flexible ablation resistance film and preparation method thereof |
| JP7045186B2 (en) * | 2017-12-28 | 2022-03-31 | ランテクニカルサービス株式会社 | Substrate joining method, transparent substrate laminate and device including substrate laminate |
| CN113667936B (en) * | 2021-09-06 | 2023-08-25 | 湖北中烟工业有限责任公司 | High-temperature antioxidant ultrathin heating film and preparation method thereof |
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 |
-
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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108430524A (en) * | 2015-11-13 | 2018-08-21 | 3M创新有限公司 | Antimicrobial articles and its application method |
| CN108430524B (en) * | 2015-11-13 | 2021-07-20 | 3M创新有限公司 | Antimicrobial articles and methods of use thereof |
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| CN102941712A (en) | 2013-02-27 |
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Address after: Wang Kau village Gaobu town Dongguan Huang Lu 523000 Guangdong Province, Beijing and Dongguan city science and Technology Park Building 1 layer B Patentee after: Dongguan Xingcheng environmental protection Mstar Technology Ltd Address before: Wang Kau village Gaobu town Dongguan Huang Lu 523000 Guangdong Province, Beijing and Dongguan city science and Technology Park Building 1 layer B Patentee before: DONGGUAN ZHENGCHENG NEW MATERIAL Co.,Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 Termination date: 20201023 |