CN113118631B - Method for removing thick coating and modifying surface of matrix based on laser shock - Google Patents
Method for removing thick coating and modifying surface of matrix based on laser shock Download PDFInfo
- Publication number
- CN113118631B CN113118631B CN202110285516.5A CN202110285516A CN113118631B CN 113118631 B CN113118631 B CN 113118631B CN 202110285516 A CN202110285516 A CN 202110285516A CN 113118631 B CN113118631 B CN 113118631B
- Authority
- CN
- China
- Prior art keywords
- coating
- laser
- matrix
- substrate
- interface
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
- C21D10/005—Modifying the physical properties by methods other than heat treatment or deformation by laser shock processing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/355—Texturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/356—Working by laser beam, e.g. welding, cutting or boring for surface treatment by shock processing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/3568—Modifying rugosity
- B23K26/3584—Increasing rugosity, e.g. roughening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/362—Laser etching
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laser Beam Processing (AREA)
Abstract
The invention provides a method for removing a thick coating and modifying the surface of a matrix based on laser shock, which comprises the following steps: etching and partitioning the coating by using a laser etching method; the coating after the partition is subjected to impact etching by using short pulse laser, so that shock waves generated by interaction of the short pulse impact laser and the surface of the coating are transmitted from the coating to the substrate, impedance mismatching at an interface is caused by different impedances of the coating and the substrate, and the intensity of tensile waves reflected at the interface exceeds the bonding strength of the interface, so that the coating is peeled off; simultaneously, the generated shock wave penetrates through the interface to act on the surface of the matrix and is used for strengthening the surface of the matrix. According to the invention, the purpose of peeling off the thick coating is realized by impacting the area to be removed; meanwhile, the laser impact induces the matrix to generate plastic deformation, so that the surface of the matrix is strengthened, the surface texture appearance is formed, the surface of the matrix is roughened, and the bonding strength between a new coating and the matrix is improved.
Description
Technical Field
The invention relates to the field of advanced laser manufacturing or the technical field of laser shock, in particular to a method for removing a thick coating and modifying the surface of a substrate based on laser shock.
Background
In engineering applications, especially the surfaces of many pieces of heavy equipment, are coated with thick coatings. For example, the aircraft skin is composed of a primer, an anti-corrosion paint layer, a finish paint and the like; the surface of various equipment working under the high-temperature thermal cycle working condition is usually provided with a thermal barrier coating and the like. The common characteristics of the coatings, whether the surface paint of the aircraft skin or the thermal barrier coating, are thick, the total thickness of the paint layer on the surface of the aircraft skin can reach several millimeters, and the thermal barrier coating can also reach hundreds of micrometers. In addition, the thick coating has very high bonding strength with the substrate due to the poor working condition of equipment, high safety factor requirement and the like. After the aircraft skin, the tank shell and the like are in service for a period of time, the surface paint can cause dominant damage or invisible damage such as falling, cracking and aging due to external force, radiation, airflow scouring and the like, and the whole or local old paint layer needs to be removed so as to coat a new coating. After the thermal barrier coating on the surface of the aircraft engine is in service for a period of time, the thermal barrier coating needs to be partially or wholly removed so as to facilitate the application of a new coating. At present, the thick coating is removed by adopting a chemical cleaning, sand blasting or manual polishing mode, and the problems of environmental pollution, low efficiency, substrate damage and the like exist. Laser cleaning is a new cleaning method that has been rapidly developed in recent years, and removes an object to be removed by using interaction between laser light and the object to be removed. The method is widely used for removing thin-layer pollutants such as rust, oxide skin, oil stain and the like, and the mechanism for removing the object to be removed by laser is as follows: the ultra-high peak power density beam of the short pulse or ultra-short pulse laser is used for acting on the fog to be removed to enable the fog to reach a gasification point, and finally the fog to be removed is removed through gasification. Such a method has the advantage that the removal to be effected can be carried out precisely. Such methods have the disadvantages of low removal efficiency, direct action on the substrate and risk of damage to the substrate. This limits the application of laser cleaning methods based on the vapor ablation mechanism to large area engineering applications and heavy engineering equipment.
Aiming at the laser cleaning technology of the aircraft skin, people also try to find methods and devices for cleaning the aluminum alloy painting material simulating the aircraft skin by using laser in some laboratories. The method for removing the aircraft skin surface coating by laser can quickly and effectively remove the paint coating on the aluminum skin surface, and achieves the aim of removing the paint coating by adjusting laser process parameters including laser output average power P, laser spot size D, laser repetition frequency f, laser scanning line width, scanning speed v, scanning longitudinal lap joint distance l and other parameters. However, the prior art still relates to the field of removing paint layers mainly by means of the thermal ablation effect of laser and the efficiency is still low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for removing a thick coating and modifying the surface of a substrate based on laser impact, wherein the method comprises the steps of impacting a region to be removed by adopting a laser impact method, and matching with the impedance mismatching characteristic of the interface between the coating and the substrate, so as to realize the purpose of peeling off the thick coating; meanwhile, the laser impact induces the matrix to generate plastic deformation, so that the surface of the matrix is strengthened, the surface texture appearance is formed, the surface of the matrix is roughened, and the bonding strength between a new coating and the matrix is improved.
The present invention achieves the above-described object by the following means.
A method for realizing thick coating removal and matrix surface reshaping modification based on laser shock comprises the following steps:
etching and partitioning the coating by using a laser etching method; the coating after the partition is subjected to impact etching by using short pulse laser, so that shock waves generated by interaction of the short pulse impact laser and the surface of the coating are transmitted from the coating to the substrate, impedance mismatching at an interface is caused by different impedances of the coating and the substrate, and the intensity of tensile waves reflected at the interface exceeds the bonding strength of the interface, so that the coating is peeled off; simultaneously, the generated shock wave penetrates through the interface to act on the surface of the matrix and is used for strengthening the surface of the matrix.
Furthermore, the size of shock wave generated by interaction of the short pulse shock laser and the surface of the coating is increased, so that the shock wave penetrates through the interface to generate micro pits on the surface of the substrate, and the roughness of the surface of the substrate is improved.
Further, the short pulse laser is a nanosecond laser.
Further, the power density of the shock wave generated by the interaction of the short pulse shock laser and the coating surface is 10 8 W/cm 2 -10 11 W/cm 2 An order of magnitude.
The invention has the beneficial effects that:
the method for removing the thick coating and modifying the surface of the substrate based on laser shock innovatively utilizes the mechanical effect of laser-induced shock waves and combines the method of the impedance mismatching characteristic between the coating and the substrate, so that the substrate is strengthened while the thick coating is removed, and the surface of the substrate is roughened. Before laser impact, a large-area coating is etched and partitioned by a laser etching method so as to ensure that a peeling area and a coating removing process are controllable. Compared with the conventional gasification ablation removal method, the method for removing the thick coating by stripping has the unique advantages of high removal efficiency and good removal effect. And laser etching is adopted for partitioning, so that the coating peeling process is controllable, and the coating peeling process is easy to combine with intelligent control. In addition, the method can also strengthen the surface of the matrix and form micro pits at the same time, thereby increasing the surface strength of the matrix and the bonding force between the sprayed new coating and the surface of the matrix. Therefore, the method is particularly suitable for removing thick coatings and has the effect of modifying the surface of a substrate.
Drawings
FIG. 1 is a schematic diagram of the method for removing the thick coating and modifying the surface of the substrate based on laser shock according to the present invention.
Fig. 2 is a graph of the results of experimental removal of the coating in the examples, fig. 2a is a cross-sectional view of the coating with the coating peeled off and the substrate exposed, fig. 2b is a cross-sectional view of the coating, and fig. 2c is a graph of the peeling effect of the coating.
1-coating; 2-a substrate; 3-short pulse laser; 4, etching a groove; 5-laser impact light spot; 6-a scan path; 7-peeling off the coating.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, without limiting the scope of the invention thereto.
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "axial," "radial," "vertical," "horizontal," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the figures, which are based on the orientation or positional relationship shown in the figures, and are used for convenience in describing the present invention and to simplify the description, but are not intended to indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be construed as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
As shown in FIG. 1, the method for removing the thick coating and modifying the surface of the substrate based on laser shock comprises the following steps:
etching and partitioning the coating 1 by using a laser etching method;
the coating after the subareas are etched by using the short pulse laser 3, so that shock waves generated by the interaction of the short pulse laser 3 and the surface of the coating 1 are transmitted from the coating 1 to the substrate, impedance mismatching at an interface is caused by the difference of the impedance of the coating 1 and the impedance of the substrate 2, and the strength of the reflected tensile waves at the interface exceeds the bonding strength of the interface, so that the coating 1 is peeled off; simultaneous generation of shock wave transmission boundaryThe surface acts on the surface of the substrate 2 for strengthening the surface of the substrate. The size of shock wave generated by the interaction of the short pulse laser 3 and the surface of the coating 1 is increased, so that the shock wave penetrates through the interface to generate micro pits on the surface of the substrate 2, and the surface roughness of the substrate is improved. The roughened substrate surface is beneficial to improving the bonding strength between a new coating and the substrate in the subsequent coating spraying process. The short pulse laser is nanosecond laser. The power density of the shock wave generated by the interaction of the short pulse shock laser and the coating surface is 10 8 W/cm 2 -10 11 W/cm 2 Orders of magnitude.
Examples
The coating 1 with the thickness of 300 mu m of ceramic and the workpiece with the substrate 2 of a stainless steel plate structure are subjected to coating removal.
Using Nd 3+ : YAG laser with wavelength of 1064nm, pulse width of 15ps, power of 10W, repetition frequency of 500KHz, scanning speed of 3000mm/s, etching grooves 4 with depth of 300 μm on the coating 1, dividing the region to be removed into regions with area of 0.01mm by etching grooves 4 2 -0.09mm 2 。
Using Nd 3+ : YAG laser adopts zigzag scanning path 6 for laser impact in the partition area under the conditions of 100W output power, 1Hz repetition frequency, 4mm diameter of laser impact spot and 50% overlap ratio. The subarea internal coating peels off from the substrate 2 under the action of laser impact to form a peeling coating 7. The spalled region is where the coating has separated from the substrate but has not fallen as shown by the dotted area in FIG. 2 a. The workpiece is photographed at an angle of 45 deg., and the cross-section of the coating is clearly visible as shown in fig. 2 b. Fig. 2c shows the coating after detachment.
It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The above-listed detailed description is only a specific description of possible embodiments of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (2)
1. A method for realizing thick coating removal and matrix surface reshaping modification based on laser shock is characterized by comprising the following steps:
etching and partitioning the coating by using a laser etching method; the coating after the partition is subjected to impact etching by using short pulse laser, so that shock waves generated by the interaction of the short pulse impact laser and the surface of the coating are transmitted from the coating to the substrate, impedance mismatching at an interface is caused by the difference of the impedance of the coating and the impedance of the substrate, and the intensity of tensile waves reflected at the interface exceeds the bonding strength of the interface, so that the coating is peeled off; simultaneously, the generated shock wave penetrates through the interface to act on the surface of the matrix and is used for strengthening the surface of the matrix;
the size of shock wave generated by interaction of the short pulse laser and the surface of the coating is increased, so that the shock wave penetrates through an interface to generate a micro pit on the surface of the substrate, and the micro pit is used for improving the roughness of the surface of the substrate; the power density of the shock wave generated by the interaction of the short pulse shock laser and the coating surface is 10 8 W/cm 2 -10 11 W/cm 2 An order of magnitude.
2. The method for achieving thick coating removal and substrate surface modification based on laser shock of claim 1, wherein the short pulse laser is a nanosecond laser.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110285516.5A CN113118631B (en) | 2021-03-17 | 2021-03-17 | Method for removing thick coating and modifying surface of matrix based on laser shock |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110285516.5A CN113118631B (en) | 2021-03-17 | 2021-03-17 | Method for removing thick coating and modifying surface of matrix based on laser shock |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113118631A CN113118631A (en) | 2021-07-16 |
CN113118631B true CN113118631B (en) | 2023-01-17 |
Family
ID=76773252
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110285516.5A Active CN113118631B (en) | 2021-03-17 | 2021-03-17 | Method for removing thick coating and modifying surface of matrix based on laser shock |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113118631B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113634902B (en) * | 2021-09-28 | 2022-05-10 | 南京航空航天大学 | Gas-assisted laser processing method for removing stealth coating on surface of airplane |
CN114603259A (en) * | 2022-01-20 | 2022-06-10 | 维达力实业(赤壁)有限公司 | Method for treating surface of curtain coating cover plate |
CN114633017A (en) * | 2022-02-15 | 2022-06-17 | 江苏大学 | Method for efficiently removing thermal barrier coating by nanosecond laser |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6197133B1 (en) * | 1999-02-16 | 2001-03-06 | General Electric Company | Short-pulse high-peak laser shock peening |
SG114560A1 (en) * | 2002-07-31 | 2005-09-28 | Inst Data Storage | A method and apparatus for cleaning surfaces |
CN104842068A (en) * | 2015-04-09 | 2015-08-19 | 江苏大学 | Method for manufacturing micro-convex points on metal surface |
CN108406090A (en) * | 2018-02-05 | 2018-08-17 | 中国航发北京航空材料研究院 | A kind of high-energy short-pulse laser processing of removal metal surface camouflage coating |
CN110640302A (en) * | 2019-09-26 | 2020-01-03 | 东华大学 | Micro-texture preparation method based on laser composite process |
CN111230309A (en) * | 2020-02-20 | 2020-06-05 | 中国航空制造技术研究院 | Novel coating cleaning method |
CN111334744A (en) * | 2020-02-18 | 2020-06-26 | 江苏大学 | Processing method for regulating and controlling micro texture on surface of thermal barrier coating bonding layer by utilizing laser impact |
CN112171068A (en) * | 2020-08-28 | 2021-01-05 | 江苏大学 | Method for efficiently removing thick coating in large area and application thereof |
CN112192029A (en) * | 2020-09-08 | 2021-01-08 | 武汉金顿激光科技有限公司 | Method for removing paint layer on inner wall surface of cylindrical member |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PT1641572E (en) * | 2003-07-08 | 2012-03-22 | Spectrum Technologies Plc | Laser removal of layer or coating from a substrate |
US20100224602A1 (en) * | 2009-03-06 | 2010-09-09 | General Electric Company | Method and system for removing thermal barrier coating |
CN107523824A (en) * | 2016-06-22 | 2017-12-29 | 中国科学院沈阳自动化研究所 | It is a kind of using reiforcing laser impact technology workpiece surface prepares coating method |
-
2021
- 2021-03-17 CN CN202110285516.5A patent/CN113118631B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6197133B1 (en) * | 1999-02-16 | 2001-03-06 | General Electric Company | Short-pulse high-peak laser shock peening |
SG114560A1 (en) * | 2002-07-31 | 2005-09-28 | Inst Data Storage | A method and apparatus for cleaning surfaces |
CN104842068A (en) * | 2015-04-09 | 2015-08-19 | 江苏大学 | Method for manufacturing micro-convex points on metal surface |
CN108406090A (en) * | 2018-02-05 | 2018-08-17 | 中国航发北京航空材料研究院 | A kind of high-energy short-pulse laser processing of removal metal surface camouflage coating |
CN110640302A (en) * | 2019-09-26 | 2020-01-03 | 东华大学 | Micro-texture preparation method based on laser composite process |
CN111334744A (en) * | 2020-02-18 | 2020-06-26 | 江苏大学 | Processing method for regulating and controlling micro texture on surface of thermal barrier coating bonding layer by utilizing laser impact |
CN111230309A (en) * | 2020-02-20 | 2020-06-05 | 中国航空制造技术研究院 | Novel coating cleaning method |
CN112171068A (en) * | 2020-08-28 | 2021-01-05 | 江苏大学 | Method for efficiently removing thick coating in large area and application thereof |
CN112192029A (en) * | 2020-09-08 | 2021-01-08 | 武汉金顿激光科技有限公司 | Method for removing paint layer on inner wall surface of cylindrical member |
Non-Patent Citations (1)
Title |
---|
脉冲激光冲击划痕无约束层的TiN涂层的实验研究;殷苏民等;《中国激光》;20100110;第37卷(第01期);第316-320页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113118631A (en) | 2021-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113118631B (en) | Method for removing thick coating and modifying surface of matrix based on laser shock | |
US20060000813A1 (en) | Laser-assisted coating removal method | |
CN111230309B (en) | Novel coating cleaning method | |
CN112171068B (en) | Method for efficiently removing thick coating in large area and application thereof | |
WO2017012184A1 (en) | Variable-light-spot multilayer staggered laser shock homogeneous enhancement method for blades | |
RU2604406C2 (en) | Method of cleaning and fining gas turbine engine blade by pulse laser | |
CN110586579B (en) | Device and method for laser cleaning and surface modification composite processing of carbon fiber composite material | |
CN110773872A (en) | Femtosecond laser precision removing method for thermal barrier coating of turbine blade | |
CN106001008A (en) | Laser cleaning method for marine paint | |
RU2471995C2 (en) | Shaping method of relief elements representing swirlers of boundary layer | |
CN109546521B (en) | Laser depainting method for polyimide coating enameled wire | |
CN105349736A (en) | Crack initiation and expansion method in restraint structural component based on laser shock peening | |
CN113732519B (en) | Design method for laser paint removal process parameters of aluminum alloy aircraft skin | |
CA2886280C (en) | Method for coating by thermal spraying with an inclined particle jet | |
CN111334744A (en) | Processing method for regulating and controlling micro texture on surface of thermal barrier coating bonding layer by utilizing laser impact | |
CN104878190A (en) | Method for restraining initiation and expansion of crack of part based on laser shock peening | |
Barradas et al. | Study of adhesion of PROTAL® copper coating of Al 2017 using the laser shock adhesion test (LASAT) | |
CN114633017A (en) | Method for efficiently removing thermal barrier coating by nanosecond laser | |
CN113718188A (en) | Novel thermal barrier coating structure and preparation method thereof | |
CN104726814A (en) | Surface pretreatment method for preparing large-thickness impact-resistance thermal spraying coating | |
CN114318195A (en) | Laser shock service life prolonging method for aluminum alloy wheel without sacrificial layer | |
CN115945465A (en) | Method for removing zirconia thermal barrier coating | |
CN115233144B (en) | Mechanical laser interactive polishing strengthening method for spray-state ceramic coating | |
CN105127665A (en) | Laser preprocessing method for remanufacturing of blade part | |
Wang et al. | Investigations on the Water-Jet Guided Laser drilling film cooling holes on the 8.5 mm-thick TBC superalloy |
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 |