CN110042371B - Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma - Google Patents
Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma Download PDFInfo
- Publication number
- CN110042371B CN110042371B CN201910438977.4A CN201910438977A CN110042371B CN 110042371 B CN110042371 B CN 110042371B CN 201910438977 A CN201910438977 A CN 201910438977A CN 110042371 B CN110042371 B CN 110042371B
- Authority
- CN
- China
- Prior art keywords
- plasma
- substrate
- thermal barrier
- barrier coating
- power supply
- 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.)
- Active
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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The invention discloses a device and a method for preparing a porous thermal barrier coating by adopting low-temperature plasma, which are mainly applied to the preparation of the coating on the surface of a cavity of an injection mold. The device comprises a plasma reaction cavity, a high-voltage power supply, a three-dimensional moving platform for placing an insert, a preheating platform, a precursor sample tank, a pore-forming agent sample tank, a gas path controller, a gas bottle, a vacuum pump, a high-voltage electrode, a ground electrode, a reaction chamber and a substrate to be processed. And discharging is generated between the high-voltage electrode and the ground electrode through a high-voltage power supply, carrier gas and exciting gas are introduced to form discharge plasma, the carrier gas respectively sends the precursor and the pore-forming agent in the solution into a plasma reaction cavity, and a porous thermal barrier coating is formed on the surface of the substrate under the action of plasma. The beneficial effects of the invention are as follows: the high-energy electrons or active free radicals are utilized to react on the surface of the substrate, so that a series of problems caused by the fact that plasma in high-temperature plasma spraying contacts the surface of the substrate to generate temperature dip are avoided.
Description
Technical Field
The invention relates to a device and a method for preparing a porous thermal barrier coating by adopting low-temperature plasma, and belongs to the technical field of mold surface treatment.
Background
The production of injection molded articles generally requires different functions and properties for the mold depending on the shape, properties, and use of the article. In the face of the harsh working environment of the mold, a coating layer is necessarily plated on the surface of the cavity of the mold to meet the performance requirements of the mold. The application of the thermal barrier coating to the surface of the die cavity is a new direction, and can play roles of protecting the die, prolonging the service life of the die, improving the fluidity of the melt, delaying the cooling time of the melt, keeping the higher and stable temperature in the die cavity, and the like.
Common mold surface treatment processes include Physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), salt bath coating treatment, build-up welding techniques, plasma thermal spray techniques, and the like. However, PVD and CVD techniques require vacuum operation, increasing reaction costs; other surface treatment techniques also have the problems of long reaction time, severe use conditions, and the like. The plasma thermal spraying has the advantages of low cost, mass production, almost no limitation on spraying materials and substrates, high bonding strength of the coating and the substrate, and the like in the aspect of preparing the coating, but the common thermal spraying technology adopts arc plasma generally, and the principle is that input powder is melted at high temperature and then sprayed on the substrate. This approach has a series of problems such as excessive porosity, overheating of the coating, excessive thermal stress from the plasma and the substrate temperature, and cracking of the coating due to the sudden drop of the plasma temperature from extremely high temperatures to room temperature.
Chinese patent CN 102534457A discloses a method for preparing a thermal barrier coating structure. The invention relates to a method for preparing a thermal barrier coating on the surface of a substrate by utilizing a plasma-physical vapor deposition technology. The working environment requires a chamber pressure of less than 1kPa, which places a limit on the working environment and increases costs. Chinese patent CN 109023205A discloses a method of spraying a thermal barrier coating with a supersonic flame. The method comprises the steps of preparing an adhesive layer by utilizing supersonic flame spraying, adding a heat stabilizer into a heat-resistant agent, uniformly mixing, and carrying out powder feeding and thermal spraying in different ways with a healing agent to obtain the crack self-healing thermal barrier coating. However, the supersonic flame spraying has high fuel consumption and high cost. Chinese patent CN 109023201A discloses a thermal barrier coating with a double-layered gradient structure and a preparation process thereof. The double-layer gradient structure provided by the invention realizes the combination of new materials/new structures, breaks through the inverse constraint relation of the thickness of a single material coating on the heat insulation capacity and the service life, and further ensures the high heat insulation, long service life and high temperature resistance collaborative design of the novel structure. The coating preparation process needs to prepare two laminated heat insulation layers, the second laminated heat insulation layer is formed by stacking N sublayers, and in the preparation process, the spraying parameters are regulated so that the heat conductivity of each sublayer is gradually decreased from inside to outside, and the heat insulation temperature of each sublayer is ensured to be the same. These conditions are difficult to realize in the process, the operation steps are complicated, and the cost is high. Chinese patent CN 108950461A discloses a method for preparing a thermal barrier coating suitable for use on the surface of iron-based superalloy. The method comprises the steps of firstly carrying out agglomeration treatment of nano feed materials, then carrying out cleaning and preheating treatment on an iron base plate, then preparing an adhesive layer, remelting the adhesive layer and carrying out spraying treatment on a ceramic layer, and finally carrying out heat treatment on a prepared coating. This method requires a lot of time to prepare the nano feed material, and the bond coat remelting requires 5 to 7 reciprocating sprays, and the Yttrium Stabilized Zirconia (YSZ) coating requires 8 to 11 reciprocating sprays. The steps are complex and the cost is high. The method is only aimed at iron-based alloy, and has low universality. Chinese patent CN 107699840A discloses a method for preparing a porous zirconia thermal barrier coating. The method directly adopts 8YSZ powder for spraying, and the melting effect of the powder in a plasma torch is poor; in addition, the method directly mixes the organic pore-forming agent with 8YSZ powder, which is easy to cause the phenomenon that the pore-forming agent is decomposed before reaching the surface of the matrix, thus leading to low pore-forming efficiency and increasing cost. Chinese patent CN 109023315A discloses a method for preparing a high bond strength thermal barrier coating on the surface of titanium alloy. The method adopts a sol-gel method and a laser cladding technology to combine to prepare the coating on the surface of the titanium alloy matrix. The method has complex operation, expensive laser cladding technical equipment and high cost.
Disclosure of Invention
Aiming at the problems, the invention provides a low-temperature plasma spraying device and a low-temperature plasma spraying method, which are used for solving the problems of die cavity surface failure and the like caused by a severe working environment by spraying a thermal barrier coating on the die surface. Unlike high temperature plasmas, low temperature plasmas decompose liquid precursor fragments using energetic electrons and reactive radicals and react at the substrate surface, thus avoiding the series of problems created by temperature dips described above. The method has the advantages of simple structure, low cost and easy mass production.
The invention aims to provide a device and a method for preparing a porous thermal barrier coating by adopting low-temperature plasma.
The aim of the invention can be achieved by the following technical scheme:
the invention generates discharge between the high-voltage electrode and the ground electrode through the high-voltage power supply, and the carrier gas and the excitation gas are introduced to form plasma discharge, the carrier gas respectively sends the precursor and the pore-forming agent in the solution into the plasma reaction cavity, and the precursor and the pore-forming agent react on the surface of the substrate under the action of plasma to form the porous thermal barrier coating.
The invention relates to a device for preparing a porous thermal barrier coating by adopting low-temperature plasma, which comprises a plasma reaction cavity, a high-voltage power supply, a three-dimensional moving platform, a preheating platform, a precursor sample pool, a pore-forming agent sample pool, a gas path controller, a gas bottle, a vacuum pump, a high-voltage electrode, a ground electrode, a reaction chamber and a substrate to be processed. The plasma reaction cavity comprises a high-voltage electrode and a ground electrode; the reaction chamber is composed of a plasma reaction cavity, a three-dimensional moving platform and a preheating platform. The high-voltage power supply is connected with the high-voltage end of the plasma reaction cavity, working gas is respectively conveyed to the precursor sample tank and the pore-forming agent sample tank through the gas bottle, and the gas flow is controlled by the gas circuit controller. Plasma is generated between the high-voltage electrode and the ground electrode, and the precursor and the pore-forming agent are simultaneously fed into the plasma reaction cavity through two paths of gases.
The vacuum pump is connected with the reaction chamber.
The substrate to be processed is placed on a preheating stage, which is placed on a three-dimensional moving platform.
The invention relates to a device for preparing a porous thermal barrier coating by adopting low-temperature plasma, which comprises the following concrete implementation steps:
step 1, cleaning the surface of a substrate to be processed;
firstly, cleaning the surface of a substrate by using dilute hydrochloric acid with the mass fraction of 5%, and then cleaning the substrate by using NaOH solution with the mass fraction of 10%;
step 2, preparing a solution precursor and a pore-forming agent solution;
ZrClO of 1mol/L configuration 2 The solution is used as a solution precursor of low-temperature plasma spraying, and then saturated sodium bicarbonate solution is prepared to be used as a pore-forming agent;
step 3, placing a substrate to be processed on a three-dimensional moving platform, adjusting the substrate to a proper position and angle, and preheating the substrate;
step 4, vacuumizing the reaction chamber (such as adopting atmospheric plasma spraying without the operation);
step 5, opening an air source, and adjusting the flow of the air;
and 6, turning on a high-voltage power supply, adjusting power supply parameters, and performing plasma discharge.
As a further improvement of the invention, the position and angle of the three-dimensional moving platform in step 3 can be continuously adjusted.
As a further improvement of the invention, the three-dimensional moving platform in the step 3 can preheat the substrate, the preheating temperature is 200-300 ℃ and the preheating time is 5-10 minutes.
As a further improvement of the invention, the flow rate of the carrier gas Ar flow rate carrying the solution precursor in the step 5 is regulated to be 1-70L/min, and the flow rate of the carrier gas Ar flow rate carrying the pore-forming agent is regulated to be 1-40L/min.
As a further improvement of the present invention, the high voltage power supply in step 6 may be a dc power supply, a radio frequency power supply, an ac power supply, a pulse power supply, or the like.
As a further improvement of the invention, the solution precursor is axially introduced from the rear end of the plasma torch and the pore-forming agent is radially introduced from the front end of the plasma torch.
As a further improvement of the invention, the shape of the electrode can be designed according to actual needs so as to meet the requirement of processing any shape surface.
The beneficial effects of the invention are as follows: the high-energy electrons or active free radicals are utilized to react on the surface of the substrate, so that a series of problems caused by the fact that plasma existing in high-temperature plasma spraying is in contact with the surface of the substrate to generate temperature dip are avoided; the device is simple, has strong operability, is easy to realize, can be used for preparing the coating on the surface of various material matrixes, and has low cost; the solution precursor is adopted for spraying, so that the spraying efficiency is high; the porosity of the coating can be adjusted by the feeding amount of the pore-forming agent; the thermal barrier coating with low thermal conductivity can be effectively prepared on the surface of the injection mold cavity.
Drawings
FIG. 1 is a schematic diagram of the composition of an apparatus for producing a porous thermal barrier coating using a low temperature plasma.
In the figure: the device comprises a 1-plasma reaction cavity, a 2-high-voltage power supply, a 3-three-dimensional moving platform, a 4-preheating platform, a 5-precursor sample cell, a 6-pore-forming agent sample cell, a 7-gas circuit controller, an 8-gas bottle, a 9-vacuum pump, a 10-high-voltage electrode, an 11-ground electrode, a 12-reaction chamber and a 13-substrate to be processed.
Detailed Description
A device for preparing a porous thermal barrier coating by adopting low-temperature plasma is shown in figure 1 and consists of a plasma reaction cavity 1, a high-voltage power supply 2, a three-dimensional moving platform 3, a preheating platform 4, a precursor sample tank 5, a pore-forming agent sample tank 6, a gas circuit controller 7, a gas bottle 8, a vacuum pump 9, a high-voltage electrode 10, a ground electrode 11, a reaction chamber 12 and a substrate 13 to be processed. The steps of the specific embodiment of the porous thermal barrier coating prepared by adopting the device are as follows:
step 1, cleaning and preprocessing the surface of a substrate to be processed:
firstly, cleaning the surface of a substrate 13 to be processed by using dilute hydrochloric acid with the mass fraction of 5%, and then cleaning by using NaOH solution with the mass fraction of 10%;
step 2, preparing a solution precursor and a pore-forming agent solution:
ZrClO of 1mol/L configuration 2 The solution is used as a solution precursor of low-temperature plasma spraying, saturated sodium bicarbonate solution is prepared again to be used as a pore-forming agent, and the solution is respectively contained in a precursor sample tank 5 and a pore-forming agent sample tank 6;
step 3, placing a substrate to be processed on a three-dimensional moving platform 3, adjusting the substrate to a proper position and angle, and preheating the substrate by a preheating platform 4 at the preheating temperature of 250 ℃ for 5 minutes; if low-pressure plasma spraying is adopted, the vacuum pump 9 is opened to vacuumize the reaction chamber 12;
step 4, opening a valve of the gas bottle 8, and adjusting the gas flow through the gas circuit controller 7:
the flow rate of the carrier gas Ar carrying the solution precursor is adjusted to 35L/min, the flow rate of the carrier gas Ar carrying the pore-forming agent is adjusted to 25L/min, and the precursor and the pore-forming agent are simultaneously fed into the plasma reaction chamber 1;
step 5, switching on a high-voltage power supply 2, regulating the voltage to 10kV, regulating the frequency to 1500Hz, regulating the pulse width to 500ns, and generating plasma between the high-voltage electrode 10 and the ground electrode 11 for coating preparation;
and 6, testing the porosity and the heat conductivity coefficient of the prepared thermal barrier coating.
Claims (6)
1. A device for preparing a porous thermal barrier coating by adopting low-temperature plasma is characterized in that: the device comprises a plasma reaction cavity, a high-voltage power supply, a three-dimensional moving platform, a preheating table, a precursor sample pool, a pore-forming agent sample pool, a gas path controller, a gas bottle, a vacuum pump, a high-voltage electrode, a ground electrode, a reaction chamber and a substrate to be processed, wherein the plasma reaction cavity comprises the high-voltage electrode and the ground electrode; the reaction chamber consists of a plasma reaction cavity, a three-dimensional moving platform and a preheating platform; the high-voltage power supply is connected with the high-voltage end of the plasma reaction cavity, working gas is respectively conveyed to the precursor sample tank and the pore-forming agent sample tank through the gas bottle, and the gas flow is controlled by the gas circuit controller; generating plasma between the high-voltage electrode and the ground electrode, and simultaneously feeding the precursor and the pore-forming agent into a plasma reaction cavity through two paths of gases; the vacuum pump is connected with the reaction chamber; placing the processed substrate on a preheating table, and placing the preheating table on a three-dimensional moving platform; the solution precursor axially enters from the rear end of the plasma spray gun, and the pore-forming agent radially enters from the front end of the plasma spray gun; the position and the angle of the three-dimensional moving platform can be continuously adjusted, and the preheating temperature of the three-dimensional moving platform for preheating the substrate is 200-300 ℃.
2. A method for preparing a porous thermal barrier coating by using low-temperature plasma, which is a device for preparing the porous thermal barrier coating by using the low-temperature plasma as claimed in claim 1, and is characterized in that: step one, cleaning the surface of a substrate to be processed; preparing a solution precursor and a pore-forming agent solution; step three, placing a substrate to be processed on a three-dimensional moving platform, adjusting the substrate to a proper position and angle, and preheating the substrate; step four, vacuumizing a reaction chamber; step five, opening an air source, and adjusting the flow of the air; and step six, turning on a high-voltage power supply, adjusting power supply parameters, and performing plasma discharge.
3. The method for preparing the porous thermal barrier coating by adopting low-temperature plasma according to claim 2, wherein the method comprises the following steps: configuration of ZrClO 2 The solution is used as a solution precursor of low-temperature plasma spraying, and saturated sodium bicarbonate solution is prepared for pore-forming agent.
4. The method for preparing the porous thermal barrier coating by adopting low-temperature plasma according to claim 2, wherein the method comprises the following steps: and thirdly, preheating the substrate by the three-dimensional moving platform for 5-10 minutes.
5. The method for preparing the porous thermal barrier coating by adopting low-temperature plasma according to claim 2, wherein the method comprises the following steps: and fifthly, regulating the flow rate of the Ar flow rate of the carrier gas carrying the solution precursor to be 1-70L/min, and regulating the flow rate of the Ar flow rate of the carrier gas carrying the pore-forming agent to be 1-40L/min.
6. The method for preparing the porous thermal barrier coating by adopting low-temperature plasma according to claim 2, wherein the method comprises the following steps: the high-voltage power supply in the step six is a direct current power supply, a radio frequency power supply, an alternating current power supply or a pulse power supply.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910438977.4A CN110042371B (en) | 2019-05-24 | 2019-05-24 | Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910438977.4A CN110042371B (en) | 2019-05-24 | 2019-05-24 | Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110042371A CN110042371A (en) | 2019-07-23 |
| CN110042371B true CN110042371B (en) | 2023-10-20 |
Family
ID=67283466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910438977.4A Active CN110042371B (en) | 2019-05-24 | 2019-05-24 | Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110042371B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327475B (en) * | 2019-07-25 | 2021-06-04 | 山东大学齐鲁医院 | Device and method for sterilizing and inhibiting bacteria of solid material |
| CN111889280B (en) * | 2020-05-26 | 2022-02-01 | 深圳第三代半导体研究院 | Surface coating method and equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660115A (en) * | 2009-09-18 | 2010-03-03 | 武汉理工大学 | Preparation method of nanometer zirconia heat barrier coating |
| CN107699840A (en) * | 2017-10-25 | 2018-02-16 | 河北工业大学 | The preparation method of porous zirconia thermal barrier coating |
| CN108611623A (en) * | 2018-06-28 | 2018-10-02 | 中国科学院电工研究所 | Inhibit the spraying coating apparatus and method of solid dielectric material secondary electron yield |
| CN209923428U (en) * | 2019-05-24 | 2020-01-10 | 北京化工大学 | Device for preparing porous thermal barrier coating by adopting low-temperature plasma |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050208337A1 (en) * | 2004-03-22 | 2005-09-22 | Ulion Nicholas E | Reduced thermal conductivity TBC by EB-PVD process to incorporate porosity |
| US10822951B2 (en) * | 2017-07-21 | 2020-11-03 | Raytheon Technologies Corporation | Suspension plasma spray abradable coating for cantilever stator |
-
2019
- 2019-05-24 CN CN201910438977.4A patent/CN110042371B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101660115A (en) * | 2009-09-18 | 2010-03-03 | 武汉理工大学 | Preparation method of nanometer zirconia heat barrier coating |
| CN107699840A (en) * | 2017-10-25 | 2018-02-16 | 河北工业大学 | The preparation method of porous zirconia thermal barrier coating |
| CN108611623A (en) * | 2018-06-28 | 2018-10-02 | 中国科学院电工研究所 | Inhibit the spraying coating apparatus and method of solid dielectric material secondary electron yield |
| CN209923428U (en) * | 2019-05-24 | 2020-01-10 | 北京化工大学 | Device for preparing porous thermal barrier coating by adopting low-temperature plasma |
Non-Patent Citations (1)
| Title |
|---|
| 王战清等.大气压低温等离子体喷涂ZrO2薄膜工艺研究.热加工工艺.2019,第48卷(第8期),第164-167页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110042371A (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20170038778A (en) | Method and apparatus for the coating and for the surface treatment of substrates by means of a plasma beam | |
| WO2021022791A1 (en) | Plasma spraying and cold spraying technology-based method for preparing a protective coating for surface of key components and parts of ic equipment | |
| CN110042371B (en) | Device and method for preparing porous thermal barrier coating by adopting low-temperature plasma | |
| CN103290361A (en) | Method for applying thermal barrier coating | |
| CN103882412A (en) | Method of preparing high-barrier film by adopting plasma jet | |
| CN112851406B (en) | Method for coating nickel or nickel alloy on surface of aluminum nitride ceramic | |
| CN103789713A (en) | Anti-oxidation MCrAlY fine-grain protective coating material and preparation method thereof | |
| CN106498350A (en) | The preparation method of sial sputtering target material | |
| CN112830814A (en) | Method for coating copper or copper alloy on surface of aluminum nitride ceramic | |
| CN209923428U (en) | Device for preparing porous thermal barrier coating by adopting low-temperature plasma | |
| CN112695266A (en) | Suspension, preparation method of coating and thermal barrier coating | |
| KR101264098B1 (en) | Horizontal equipment for plasma thermal spray and horizontal plasma thermal spraying method thereby | |
| CN110773741A (en) | Preparation method of copper-aluminum composite metal material and composite metal material | |
| KR20210086194A (en) | Plazma Powder Deposition Apparatus and Deposition Method Using The Same | |
| CN114405797B (en) | Graphene coating based on liquid material plasma spraying technology and spraying process thereof | |
| CN103132007B (en) | Y prepared by low-pressure plasma spraying technology2O3Method for coating ceramic | |
| CN213507160U (en) | Thermal barrier coating device | |
| CN110158018B (en) | Al/AlN composite coating and preparation method thereof | |
| CN104711503A (en) | Boron carbide gradient coating applied to quartz substrate and preparation method thereof | |
| CN1290624C (en) | Multicomponent atmosphere controllable spraying method and apparatus | |
| JP5842766B2 (en) | Plasma coating method and apparatus | |
| KR20100109245A (en) | Deposition apparatus and method thereof | |
| CN110616394A (en) | Preparation method for improving thermal shock resistance of double-ceramic-layer TBCs | |
| CN118222969B (en) | Solid-solid lubrication silver coating with low oxidation, high density structure and long lubrication life, preparation method thereof and coated workpiece | |
| US20110146576A1 (en) | Systems for applying a thermal barrier coating to a superalloy substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |