CN105886994A - Method for manufacturing high-performance layered thermal barrier coating system - Google Patents
Method for manufacturing high-performance layered thermal barrier coating system Download PDFInfo
- Publication number
- CN105886994A CN105886994A CN201610228040.0A CN201610228040A CN105886994A CN 105886994 A CN105886994 A CN 105886994A CN 201610228040 A CN201610228040 A CN 201610228040A CN 105886994 A CN105886994 A CN 105886994A
- Authority
- CN
- China
- Prior art keywords
- thermal barrier
- barrier coating
- adhesive linkage
- alloy
- coating system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The invention discloses a method for manufacturing a high-performance layered thermal barrier coating system. The method comprises the following steps that firstly, an alloy bonding layer is manufactured on the surface of a matrix; secondly, supersonic plasma jet is used for carrying out surface modification treatment on the alloy bonding layer; and thirdly, a single-layer or multi-layer ceramic material coating is manufactured on the modified surface of the alloy bonding layer, and the thermal barrier coating system is obtained. An internal powder feeding supersonic air plasma spraying method is adopted for obtaining the layered thermal barrier coating system formed by the high-temperature alloy bonding layer and a ceramic surface layer. Compared with a traditional method for manufacturing a thermal barrier coating, the problems that due to technological conversion, the coating manufacturing efficiency is low, and the quality batch stability is poor are effectively avoided, important application value for prolonging the high-temperature service life of the a thermal barrier coating is achieved, wide application prospects are achieved in the national defense sophisticated industry such as aeroturbine engines and heavy duty gas turbines, and huge economic and social benefits are achieved.
Description
Technical field
The present invention relates to Thermal Barrier Coating Technologies field, particularly to a kind of method preparing high-performance level thermal barrier coating system.
Background technology
Aero-turbine and heavy duty gas turbine need badly a kind of high-performance thermal barrier coating system reducing alloy substrate temperature thus
Ensure that it the most normally uses.Thermal barrier coating system includes alloy adhesive linkage, ceramic layer and is aoxidized by alloy adhesive linkage
And the thermally grown oxide layer formed (TGOs).This thermal growth oxide at early growth period mainly with aluminium oxide (Al2O3) it is
Main, fine and close Al2O3Thin film plays certain positive role to the oxidation further stoping alloy coat.But Al2O3Thin film is in shape
While one-tenth, some other oxide such as chromium oxide (Cr2O3), nickel oxide (NiO) and spinelle (NiAl2O4、NiCr2O4、
CoAl2O4、CoCr2O4) etc. grown the most simultaneously.These oxides and Al2O3Compare and there is the higher speed of growth, cause
Produce substantial amounts of growth stress in TGOs/ ceramic layer interface, especially when TGOs reaches certain thickness, at above-mentioned interface and
Cause germinating and the extension of crackle inside TGOs, ultimately result in the inefficacy of the peeling of ceramic surface, i.e. thermal barrier coating.Alloy at present
The conventional preparation technology of adhesive linkage has vacuum plasma spray coating (Vacuum Plasma Spraying, VPS), low-voltage plasma to spray
Painting (Low-Pressure Plasma Spraying, LPPS), HVAF (High Velocity Oxygen Fuel, HVOF),
Cold air power spraying and coating (Cold Gas Dynamic Spraying, CGDS or CS).The preparation technology of ceramic layer is then electron beam
Physical vapour deposition (PVD) (Electron Beam Physical Vapor Deposition, EB-PVD) and air plasma spraying (Air
Plasma Spraying, APS) two kinds.Glue there it can be seen that existing thermal barrier coating system needs differently to prepare alloy
Connect layer and ceramic layer, the problem that this production efficiency that will necessarily relate to bring because of technique conversion reduces, it is unfavorable for producing continuously.
The conversion of spraying coating process simultaneously is also easily caused alloy adhesive linkage surface contamination.
Summary of the invention
It is an object of the invention to provide a kind of method preparing high-performance level thermal barrier coating system, with obtain steady quality reliable,
The thermal barrier coating system that high temperature oxidation resistance is excellent, thermal shock resistance is excellent, by the alloy of the different no cofusing particle ratio of design
Adhesive linkage and alloy adhesive linkage carries out surface modification treatment to improve its high temperature oxidation resistance, alloy the most after modification is bonding
Layer surface deposits monolayer or double-layer ceramic layer thus forms complete thermal barrier coating system.
For reaching object above, the present invention adopts the technical scheme that:
A kind of method preparing high-performance level thermal barrier coating system, comprises the following steps: the first step, prepares alloy at matrix surface
Adhesive linkage；Second step, utilizes supersonic speed plasma jet that alloy adhesive linkage is carried out surface modification treatment；3rd step, in modification
After alloy adhesive linkage surface prepare single or multiple lift ceramic coating, it is thus achieved that thermal barrier coating system.
Further, the first step specifically includes following steps: use internal powder conveying supersonic speed air plasma spraying spray gun spraying alloy to glue
Connecing layer, in spraying process, power adjustments is 80-140mm to 25-70kW, spray distance scope, controls alloy in spraying process
Flying speed of partcles scope is 350-550m/s, and temperature range is 1900-2600 DEG C, it is thus achieved that no cofusing particle content is 5-60%'s
Alloy adhesive linkage；The alloy adhesive linkage material that internal powder conveying supersonic speed air plasma spraying spray gun is sprayed be CoNiCrAlY,
NiCoCrAlY or NiCrAlY.
Further, second step specifically includes following steps: use internal powder conveying supersonic speed air plasma spraying spray gun without powder feeding shape
Scanning established alloy adhesive linkage surface continuously under state, power is 30-100kW, and distance is 70-150mm, number of times
For 10-50 time.
Further, second step utilizes the high temperature during internal powder conveying supersonic speed air plasma spraying, supersonic speed at a high speed etc. from
Daughter jet is by alloy adhesive linkage surface melting and forms fine and close oxide skin(coating), will stick to not melting of alloy adhesive linkage surface simultaneously
Granule is removed.
Further, in the 3rd step, ceramic layer is prepared on alloy adhesive linkage surface after modification, and ceramic layer is: yittrium oxide is partially stabilized
Zirconium dioxide single-layer ceramic layer, YSZ-lanthanum cerate double-layer ceramic layer or YSZ-lanthanum magnalium oxygen (LaMA) double-layer ceramic layer.
Further, power selection when using internal powder conveying supersonic speed air plasma spraying method to prepare ceramic layer in the 3rd step exists
30-80kW, spray distance scope is 80-120mm, and controlling ceramic particle flight speed scope in spraying process is 340-800m/s,
Temperature range is 2000-3600 DEG C.
Relative to prior art, the method have the advantages that the method according to the present invention, can high-efficiency and continuous deposition quality steady
Determine the thermal barrier coating system reliable, high temperature oxidation resistance is excellent, thermal shock resistance is excellent, in aero-turbine and heavy type
The national defence sophisticated industries such as gas turbine have broad application prospects.
Accompanying drawing explanation
Fig. 1 be embodiment 1 no cofusing particle content be the alloy adhesive linkage section erosion profile of 35%；
Fig. 2 is that embodiment 1 sprays state alloy adhesive linkage surface topography；
Fig. 3 is alloy adhesive linkage surface topography after embodiment 1 supersonic speed plasma jet surface modification；
Fig. 4 is embodiment 1 thermal barrier coating system section pattern；
Fig. 5 is the oxidizing dynamics curve at embodiment 1 coating 1100 DEG C；
Fig. 6 is the surface topography under embodiment 1 coating 1100 DEG C, different thermal shock number of times.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of method preparing high-performance level thermal barrier coating system, using CoNiCrAlY alloy powder is raw material, send in employing
Powder supersonic speed air plasma spraying spray gun spraying alloy adhesive linkage, in spraying process, power adjustments to 54.8kW, spray distance is
110mm, uses the alloy powder grain in high-speed photography and dual wavelength radiation intensity rate method plasma jet in spraying process
Sub-flight speed and temperature carry out on-line measurement, and the flying speed of partcles obtained is 420m s-1, temperature is 2330 DEG C, to alloy
Carry out scanning electron microscopic observation after adhesive linkage corrosion, the coating profile pattern that obtains as it is shown in figure 1, surface topography as shown in Figure 2.Adopt
Analyzing no cofusing particle content in coating with image processing software is 35%.Utilize supersonic speed plasma jet to alloy adhesive linkage table
Face carries out processing (power is 50kW, and distance is 90mm, laser heating 50 times), and the coating morphology after process adds Fig. 3
Shown in, comparison diagram 2 and Fig. 3 is it is found that supersonic speed plasma jet can remove spraying state alloy adhesive linkage surface adhesion
No cofusing particle, improves the surface smoothness of alloy adhesive linkage.Alloyed layer spraying YSZ ceramic layer after surface modification,
Constituting complete thermal barrier coating system, its profile is as shown in Figure 4.Coating system is carried out 1100 DEG C of high-temperature oxydation experiments and heat
Impact experiment, result respectively the most as shown in Figures 5 and 6, therefrom it appeared that after to alloy adhesive linkage surface modification, can be obvious
Improving the high temperature oxidation resistance of coating, show as its increasing weight of oxidation relatively low, this thermal barrier coating system is 1100 DEG C of insulations
Hardening after 5 points, only has the area of 9.3% to peel off 846 rear surfaces, shows compared with the coating of long time without surface modification treatment
Good thermal shock resistance.
Table 1 alloy adhesive linkage spray parameters and the flying speed of partcles of correspondence, surface temperature and no cofusing particle content
Internal powder conveying supersonic speed air plasma spraying is a kind of novel plasma spraying technology, and its ultimate principle is to utilize gun system,
By mechanical compress, hot compression and magnetic compression, electric arc is elongated, and then the supersonic speed plasma obtaining having very high energies density is penetrated
Stream, and make the material powder particle heated fast entering in jet fusing clash into matrix and form coating.Utilize internal powder conveying supersonic speed
Atmospheric plasma spraying technology deposit alloy adhesive linkage and ceramic layer, it is not necessary to technique is changed, thus drastically increases spray efficiency.
Meanwhile, present stage carries out surface and processes the method mostly using heating in vacuum alloy adhesive linkage, it is therefore an objective to its surface formed with
Aluminium oxide is main oxide skin(coating), thus reduces alloy adhesive linkage oxidation rate under the conditions of high-temperature service.Use application of vacuum,
Accessory size will be limited by vacuum chamber, greatly limit the application of the method.Utilize supersonic speed plasma jet high temperature and high speed
Feature, carries out surface modification treatment to alloy adhesive linkage in atmospheric conditions so that it is while surface forms oxide, again can be by table
The no cofusing particle that face adheres to is removed.In a word, use the internal powder conveying supersonic speed air plasma spraying can be with deposit alloy adhesive linkage, involutory
Gold adhesive linkage modifying surface processes and prepares ceramic layer, can be continuously produced, and coating quality is reliable and stable.
By the present invention, finally obtain the thermal boundary that steady quality is reliable, high temperature oxidation resistance is excellent, thermal shock resistance is excellent and be coated with
Coating systems, has broad application prospects in the national defence sophisticated industry such as aero-turbine and heavy duty gas turbine.
Claims (6)
1. the method preparing high-performance level thermal barrier coating system, it is characterised in that comprise the following steps:
The first step, uses internal powder conveying supersonic speed air plasma spraying spray gun to prepare alloy adhesive linkage at matrix surface；
Second step, utilizes supersonic speed plasma jet that alloy adhesive linkage is carried out surface modification treatment；
3rd step, single or multiple lift ceramic coating is prepared on alloy adhesive linkage surface after modification, it is thus achieved that complete thermal barrier coating
System.
A kind of method preparing high-performance level thermal barrier coating system the most according to claim 1, it is characterised in that first
Step specifically includes following steps: use internal powder conveying supersonic speed air plasma spraying spray gun spraying alloy adhesive linkage, merit in spraying process
Rate regulates to 25-70kW, and spray distance scope is 80-140mm, controls alloy particle flight speed scope and be in spraying process
350-550m/s, temperature range is 1900-2600 DEG C, it is thus achieved that no cofusing particle content is at the alloy adhesive linkage of 5-60%；Internal powder conveying
The alloy adhesive linkage material that supersonic speed air plasma spraying spray gun is sprayed is CoNiCrAlY, NiCoCrAlY or NiCrAlY.
A kind of method preparing high-performance level thermal barrier coating system the most according to claim 1, it is characterised in that second
Step specifically includes following steps: use internal powder conveying supersonic speed air plasma spraying spray gun to established alloy under without powder feeding state
Adhesive linkage surface is scanned continuously, and power is 30-100kW, and distance is 70-150mm, and number of times is 10-50 time.
A kind of method preparing high-performance level thermal barrier coating system the most according to claim 3, it is characterised in that second
Step utilize the high temperature during internal powder conveying supersonic speed air plasma spraying, supersonic speed plasma jet at a high speed alloy is bonding
Layer surface melting also forms fine and close oxide skin(coating), and the no cofusing particle that simultaneously will stick to alloy adhesive linkage surface is removed.
A kind of method preparing high-performance level thermal barrier coating system the most according to claim 1, it is characterised in that the 3rd
In step, ceramic layer is prepared on alloy adhesive linkage surface after modification, and ceramic layer is: the zirconium dioxide single-layer ceramic that yittrium oxide is partially stabilized
Layer, YSZ-lanthanum cerate double-layer ceramic layer or YSZ-lanthanum magnalium oxygen (LaMA) double-layer ceramic layer.
A kind of method preparing high-performance level thermal barrier coating system the most according to claim 1, it is characterised in that the 3rd
Power selection when using internal powder conveying supersonic speed air plasma spraying method to prepare ceramic layer in step is at 30-80kW, spray distance
Scope is 80-120mm, and controlling ceramic particle flight speed scope in spraying process is 340-800m/s, and temperature range is
2000-3600℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610228040.0A CN105886994B (en) | 2016-04-13 | 2016-04-13 | A method of preparing high-performance level thermal barrier coating system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610228040.0A CN105886994B (en) | 2016-04-13 | 2016-04-13 | A method of preparing high-performance level thermal barrier coating system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105886994A true CN105886994A (en) | 2016-08-24 |
| CN105886994B CN105886994B (en) | 2018-09-04 |
Family
ID=57012546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610228040.0A Active CN105886994B (en) | 2016-04-13 | 2016-04-13 | A method of preparing high-performance level thermal barrier coating system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105886994B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108060384A (en) * | 2017-12-12 | 2018-05-22 | 中国航发沈阳黎明航空发动机有限责任公司 | A kind of double ceramic layer thermal barrier coating systems and its composite-making process |
| CN108728786A (en) * | 2018-04-11 | 2018-11-02 | 中国人民解放军陆军装甲兵学院 | A method of preparing silumin coating |
| CN108950461A (en) * | 2018-06-30 | 2018-12-07 | 黑龙江科技大学 | A kind of preparation method suitable for iron base high-temperature alloy surface thermal barrier coating |
| CN109317376A (en) * | 2017-07-31 | 2019-02-12 | 通用电气公司 | Coated component and the method for forming coating system on the surface of the substrate |
| CN110541138A (en) * | 2019-10-09 | 2019-12-06 | 西安热工研究院有限公司 | Interlayer metallurgical bonding thermal spraying coating for boiler heating surface and preparation method |
| CN111962005A (en) * | 2020-09-09 | 2020-11-20 | 上海电气集团股份有限公司 | Preparation method of thermal barrier coating |
| CN114438435A (en) * | 2022-01-24 | 2022-05-06 | 西南科技大学 | Thermal barrier coating and preparation method thereof |
| CN115354268A (en) * | 2022-08-31 | 2022-11-18 | 西安航空学院 | Method for involuting Jin Nianjie layer surface modification by supersonic plasma jet |
| CN116254496A (en) * | 2022-09-09 | 2023-06-13 | 北京金轮坤天特种机械有限公司 | Preparation method of thermal barrier coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789715A (en) * | 2014-02-10 | 2014-05-14 | 江苏大学 | Anti-oxidization thermal barrier coating material with long service life and preparation method thereof |
-
2016
- 2016-04-13 CN CN201610228040.0A patent/CN105886994B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789715A (en) * | 2014-02-10 | 2014-05-14 | 江苏大学 | Anti-oxidization thermal barrier coating material with long service life and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 唐健江等: "热障涂层体系中MCrAlY 合金粘接层结构设计及高温氧化行为研究", 《热喷涂技术》 * |
| 徐滨士等: "《材料表面工程技术》", 31 December 2014, 哈尔滨工业大学出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317376A (en) * | 2017-07-31 | 2019-02-12 | 通用电气公司 | Coated component and the method for forming coating system on the surface of the substrate |
| CN108060384A (en) * | 2017-12-12 | 2018-05-22 | 中国航发沈阳黎明航空发动机有限责任公司 | A kind of double ceramic layer thermal barrier coating systems and its composite-making process |
| CN108728786A (en) * | 2018-04-11 | 2018-11-02 | 中国人民解放军陆军装甲兵学院 | A method of preparing silumin coating |
| CN108950461A (en) * | 2018-06-30 | 2018-12-07 | 黑龙江科技大学 | A kind of preparation method suitable for iron base high-temperature alloy surface thermal barrier coating |
| CN110541138A (en) * | 2019-10-09 | 2019-12-06 | 西安热工研究院有限公司 | Interlayer metallurgical bonding thermal spraying coating for boiler heating surface and preparation method |
| CN111962005A (en) * | 2020-09-09 | 2020-11-20 | 上海电气集团股份有限公司 | Preparation method of thermal barrier coating |
| CN114438435A (en) * | 2022-01-24 | 2022-05-06 | 西南科技大学 | Thermal barrier coating and preparation method thereof |
| CN114438435B (en) * | 2022-01-24 | 2023-08-25 | 西南科技大学 | Thermal barrier coating and preparation method thereof |
| CN115354268A (en) * | 2022-08-31 | 2022-11-18 | 西安航空学院 | Method for involuting Jin Nianjie layer surface modification by supersonic plasma jet |
| CN116254496A (en) * | 2022-09-09 | 2023-06-13 | 北京金轮坤天特种机械有限公司 | Preparation method of thermal barrier coating |
| CN116254496B (en) * | 2022-09-09 | 2023-12-15 | 北京金轮坤天特种机械有限公司 | Preparation method of thermal barrier coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105886994B (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105886994A (en) | Method for manufacturing high-performance layered thermal barrier coating system | |
| US6054184A (en) | Method for forming a multilayer thermal barrier coating | |
| US8007899B2 (en) | Segmented abradable coatings and process(es) for applying the same | |
| EP1642993B1 (en) | Segmented gadolinia zirconia coatings | |
| CN105951028B (en) | A kind of method of synchronous powder feeding system preparation continuous gradation structural ceramics base thermal barrier coating | |
| CN107699840A (en) | The preparation method of porous zirconia thermal barrier coating | |
| EP0969117A2 (en) | Method of forming a thermal barrier coating system | |
| CN106119760B (en) | A kind of thermal barrier coating and preparation method thereof with the double-deck adhesive layer | |
| US5759640A (en) | Method for forming a thermal barrier coating system having enhanced spallation resistance | |
| US20110048017A1 (en) | Method of depositing protective coatings on turbine combustion components | |
| CN105779925B (en) | The method that supersonic flame spraying fore-put powder carries out laser melting coating | |
| CN109628929A (en) | A kind of thermal barrier coating and the preparation method and application thereof, aero engine turbine blades | |
| CN109706418A (en) | A kind of double ceramic layer structure 8YSZ thermal barrier coatings and preparation method | |
| CN110144541B (en) | High-temperature titanium alloy thermal barrier coating material and preparation method thereof | |
| US6180260B1 (en) | Method for modifying the surface of a thermal barrier coating, and related articles | |
| CN113151772A (en) | Novel high-temperature corrosion-resistant thermal barrier coating with double ceramic layer structure and preparation method thereof | |
| CN109440046A (en) | A kind of aero-engine and gas turbine blades thermal barrier coating and preparation method thereof | |
| US20080044663A1 (en) | Dual layer ceramic coating | |
| CN106011721B (en) | A method of laminated coating is prepared using hot spray process | |
| CN111962028A (en) | EB-PVD/APS composite structure double-ceramic-layer thermal barrier coating and preparation method thereof | |
| US20180282853A1 (en) | Hybrid Thermal Barrier Coating and Process of Making Same | |
| CN116445911A (en) | Preparation method of thermal barrier coating | |
| CN110616394A (en) | Preparation method for improving thermal shock resistance of double-ceramic-layer TBCs | |
| CN109161835A (en) | A kind of method that surface of hot die steel prepares AlCrTiN/WC-12Co composite coating | |
| CN115354268A (en) | Method for involuting Jin Nianjie layer surface modification by supersonic plasma jet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |