CN107723663B - A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony - Google Patents
A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony Download PDFInfo
- Publication number
- CN107723663B CN107723663B CN201710881086.7A CN201710881086A CN107723663B CN 107723663 B CN107723663 B CN 107723663B CN 201710881086 A CN201710881086 A CN 201710881086A CN 107723663 B CN107723663 B CN 107723663B
- Authority
- CN
- China
- Prior art keywords
- antimony
- strength steel
- heater
- adsorbent
- evaporation
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/26—Vacuum evaporation by resistance or inductive heating of the source
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- 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
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
- C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to a kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony.By being heated at high temperature metallic antimony; gasification and antimony molecule deposition are allowed to the lower surface of steel plate of temperature; form fine and close solid protective film; the problem of making platability be deteriorated because of surface generation selective oxidation when fundamentally improving continuous zinc coating; guarantee is provided to provide high hot dip plated steel quality, there is considerable Social benefit and economic benefit.
Description
Technical field
The present invention relates to galvanizing by dipping technical field, it is related to a kind of method before annealing in high strength steel surface preparation,
Specifically, referring to a kind of method in three hole continuous vacuum evaporation metal antimony of high strength steel surface.
Background technique
Vacuum vapor plating (vapor deposition) is that under vacuum conditions, heating evaporation substance is allowed to gasify and is deposited on substrate surface
Solid film is formed, is a kind of physical phenomenon.It is widely used in machinery, electrovacuum, radio, optics, atomic energy, space skill
The fields such as art.Its oxidation potential of metallic antimony is lower than iron, and oxidation reaction when annealing is not related to the element substantially.Meanwhile the steam of antimony
Press higher, in vacuum environment, antimony vapour pressure corresponding to 677 DEG C is 10-2Torr。
Galvanizing by dipping is that steel component immerses in the zinc liquid of melting a kind of method for obtaining metal cladding.With high pressure
Transmission of electricity, traffic, communication career rapidly develop, also higher and higher to the quality requirement of galvanizing by dipping.Currently, being applied to industrial production
Continuous zinc coating method there are many kinds of, such as Sendzimir method, U.S. steel join method, Wheeling method, Selas method.
But major part galvanizing production is produced by Sendzimir method at present.Typical Sendzimir method, steel plate are necessary
Through over cleaning, to remove cold rolling, the oil on surface, carbon and ferrous powder granules.The solution of cleaning is usually 1.5%~2.5% NaOH
Solution.Next steel plate is dried up with low-pressure gas.Then it enters back into heating and heat preservation zone carries out recrystallization annealing.From annealing furnace
After out, steel plate is cooled to the temperature of slightly above zinc pond (460 DEG C), is then immersed in zinc pond.
It is well known that, since temperature is excessively high, steel and active gases can occur very in the annealing stage of continuous zinc coating line
Complicated reaction, wherein so-called selective oxidation will occur for the alloying element of surface of steel plate;" selective oxidation " refers in steel
With the stronger alloying element of oxygen affinity prior to the behavior of matrix Fe Element generation oxide.And in DP steel, due to Si,
The selective oxidation of the alloying elements such as Mn, surface of steel plate cover the oxide of these alloying elements, and platability can be deteriorated.Institute
With aiming at the problem that DP steel platability is deteriorated, it is necessary to find and reduce the effective way that selective oxidation occurs for its surface.
Summary of the invention
The present invention is intended to provide one kind is easy to operate, economical and practical and is adapted to industrial quantity-produced high strength steel annealing
Preceding preprocess method is allowed to gasification and antimony molecule deposition to the lower surface of steel plate of temperature, shape by being heated at high temperature metallic antimony
At fine and close solid protective film, as shown in Figure 1, 2, implementation through the invention can effectively reduce the selective oxygen of surface of steel plate
Change, makes oxide on surface SiO2, MnO and Mn-Si composite oxides significantly reduce, enhancing later period zinc-plated platability.
The technical solution that the present invention implements its purpose is:
A kind of device and method in three hole continuous vacuum evaporation metal antimony of high strength steel surface, are technically characterized in that
Vacuum vapor plating pre-processes high strength steel, and oxide when high strength steel being made to anneal significantly reduces, and specific steps are such as
Under:
1. entire vapor deposition process carries out in a vacuum chamber, vacuum degree is 1 × 10-2Pa。
2. the matrix of high strength steel is iron, trace additives include carbon, silicon, manganese, chromium.
3. vapor deposition described device includes: vacuum chamber, detection contact pilotage and three hole antimony regulus vaporization chambers;Three hole antimony regulus vaporization chambers are located at
In vacuum chamber wall body, along high-strength steel sheet mirror symmetry, face centered on the high-strength steel sheet for occuping entire vacuum chamber center
The two-sided two sides of high strength steel, be divided into left side vaporization chamber and right side vaporization chamber, structure are identical: left side vaporization chamber includes vaporization chamber wall
Body, around resistance band, adsorbent, adsorbent heater, temperature measurer, evaporation source antimony regulus, evaporation heater, cooling circulating water, absolutely
Edge substrate.Vaporization chamber wall bottom end is equipped with dielectric base, and dielectric base is equipped with evaporation source antimony regulus, and evaporation source antimony regulus is surrounded by
Evaporation heater, is equipped with cooling circulating water between evaporation source antimony regulus and dielectric base, evaporation heater is equipped with temperature measurer, is steaming
Wall outer side is placed equidistant with three tongues with holes on the right side of hair room, and tongue is equipped with tongue mouth, nestles up wall on the right side of vaporization chamber
Outside is scattered adsorbent and adsorbent heater, and adsorbent and adsorbent heater abut, and substrate heater is against high-strength
Steel plate is spent, detection contact pilotage contacts detection below steel plate with steel plate.The evaporation heater is frequency spiral coil;The absorption
Agent heater is electromagnetic heater;The substrate heater is around resistance band.
Tongue uses square structure, is highly 50~70 ㎝, width is bigger by 5~10 than the high strength steel board width of required vapor deposition
㎝。
Tongue mouth uses square structure, is highly 5~10 ㎝, width is consistent with tongue.
High-strength steel sheet is 15 ㎝ at a distance from tongue with holes.
4. the adsorbent Zr-16Al of vaporization chamber wall outer side is preheated 3 hours at 800 DEG C using adsorbent heater,
Active gases in vacuum chamber is removed, steel plate and antimony regulus are in room temperature at this time, after the completion of absorption, stop the heating of adsorbent.
5. keeping the temperature substrate steel disc around resistance band using evaporation heater by evaporation source antimony regulus in 677 DEG C of continuous heatings
At low temperature (230~300 DEG C).
6. high-strength steel sheet slow transits through left and right sides tongue spray antimony mouth in three times from top to bottom, right at 677 DEG C using antimony
Answering vapour pressure is 10-2Torr, the characteristic that evaporation effect is optimal and high temperature atomic can be moved to low temperature face are covered high strength steel is two-sided
Cover uniform antimony protective film.
7. the steel plate after the completion of cooling utilizes detection contact pilotage detection vapor deposition film thickness.
The specific implementation step of described device are as follows:
The adsorbent Zr-16Al of vaporization chamber wall outer side is preheated 3 hours at 800 DEG C using adsorbent heater, is gone
Except active gases in vacuum chamber, steel plate and antimony regulus are in room temperature at this time, after the completion of absorption, stop the heating of adsorbent.
Using evaporation heater by evaporation source antimony regulus in 677 DEG C of continuous heatings, while utilizing cooling circulating water regulation mutation
Temperature makes the heat preservation of substrate steel disc at low temperature (230~300 DEG C), observes the variation of temperature measurer registration around resistance band.
Driving device, which generates driving force, makes high-strength steel sheet slow transit through left and right sides tongue spray antimony in three times from top to bottom
Mouthful, it is 10 using saturated vapour pressure-2The characteristic that Torr evaporation effect is optimal and high temperature atomic can be moved to low temperature face, will be high-intensitive
The uniform antimony protective film of the two-sided covering of steel.
Steel plate after the completion of cooling utilizes detection contact pilotage detection vapor deposition film thickness.
When replacing antimony regulus, it need to stop heating, after the completion of replacement, restart from step 1.
The method of three hole continuous vacuum evaporation metal antimony of high strength steel surface of the invention, provides one for continuous hot-dipping galvanizing
The pretreated method of kind, the oxide on surface, preprocessing process are completed in a vacuum chamber when reducing zinc-plated.Fundamentally improve
It the problem of making platability be deteriorated because of surface generation selective oxidation when continuous zinc coating, is provided to provide high hot dip plated steel quality
Guarantee that there is considerable Social benefit and economic benefit.
Detailed description of the invention
Attached drawing described herein as is used to be further explained the present invention, constitutes part of this application, of the invention shows
Meaning property diagram is used to explain the present invention, and is not constituted improper limitations of the present invention, protection scope of the present invention is not limited to following
Schematic diagram.
Fig. 1 is the high strength steel surface FE-SEM figure of 1000 times of completion evaporation metal antimony.
Fig. 2 is the high strength steel surface FE-SEM figure of 10000 times of completion evaporation metal antimony.
Fig. 3 is internal vacuum chamber schematic device.
Drawing reference numeral
[1] dielectric base [2] cooling circulating water [3] evaporation source antimony regulus
[4] frequency spiral coil [5] temperature measurer [6] electromagnetic heater
[7] adsorbent [8] is around resistance band [9] high-strength steel sheet
[10] tongue sprays antimony mouth [11] tongue [12] vacuum chamber wall
[13] vaporization chamber wall [14] detects contact pilotage
Specific embodiment
Specifically introduce the present embodiment with reference to the accompanying drawing to elaborate: the present embodiment is being with technical solution of the present invention
Under the premise of implemented, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments.
The adsorbent 7 of vaporization chamber wall outer side is preheated 3 hours at 800 DEG C using electromagnetic heater 6, removes vacuum chamber
Interior active gases, steel plate 9 and antimony regulus 3 are in room temperature at this time, after the completion of absorption, stop the heating of adsorbent.
Using frequency spiral coil 4 by evaporation source antimony regulus 3 in 677 DEG C of continuous heatings, while being regulated and controled using cooling circulating water 2
Abrupt temp makes the heat preservation of substrate steel disc 9 at low temperature (230~300 DEG C), observes the variation of 5 registration of temperature measurer around resistance band 8.
Driving device, which generates driving force, makes high-strength steel sheet 9 slow transit through left and right sides tongue 11 in three times from top to bottom
Tongue sprays antimony mouth 10, is 10 using saturated vapour pressure-2The spy that Torr evaporation effect is optimal and high temperature atomic can be moved to low temperature face
Property, by the uniform antimony protective film of the two-sided covering of high strength steel.
Steel plate 9 after the completion of cooling utilizes the detection detection vapor deposition film thickness of contact pilotage 14.
The method of three hole continuous vacuum evaporation metal antimony of high strength steel surface of the invention, provides one for continuous hot-dipping galvanizing
The pretreated method of kind, the oxide on surface, preprocessing process are completed in a vacuum chamber when reducing zinc-plated.Fundamentally improve
It the problem of making platability be deteriorated because of surface generation selective oxidation when continuous zinc coating, is provided to provide high hot dip plated steel quality
Guarantee that there is considerable Social benefit and economic benefit.
Claims (6)
1. a kind of device in high strength steel surface continuous vacuum evaporation metal antimony, it is characterised in that: described device includes: vacuum
Room, detection contact pilotage and three hole antimony regulus vaporization chambers;Three hole antimony regulus vaporization chambers are located in vacuum chamber wall body, to occupy in entire vacuum chamber
Along high-strength steel sheet mirror symmetry centered on the high-strength steel sheet of centre, the two-sided two sides of face high strength steel are divided into left side vaporization chamber
With right side vaporization chamber, structure is identical: left side vaporization chamber includes vaporization chamber wall, around resistance band, adsorbent, adsorbent heating
Device, temperature measurer, evaporation source antimony regulus, evaporation heater, cooling circulating water, dielectric base;Vaporization chamber wall bottom end is equipped with insulation base
Bottom, dielectric base are equipped with evaporation source antimony regulus, and evaporation source antimony regulus is surrounded by evaporation heater, evaporation source antimony regulus and dielectric base
Between be equipped with cooling circulating water, evaporation heater be equipped with temperature measurer, wall outer side is placed equidistant with three bands on the right side of vaporization chamber
Hole tongue, tongue are equipped with tongue mouth, nestle up and are scattered adsorbent and adsorbent heating on the right side of vaporization chamber on the outside of wall
Device, adsorbent and adsorbent heater abut, substrate heater abut high-strength steel sheet, detect contact pilotage below steel plate with steel plate
Contact detection;Entire vapor deposition process carries out in a vacuum chamber, and vacuum degree is 1 × 10-2Pa。
2. a kind of device in high strength steel surface continuous vacuum evaporation metal antimony as described in claim 1, it is characterised in that:
The evaporation heater is frequency spiral coil;The adsorbent heater is electromagnetic heater;The substrate heater is ring
Around resistance band.
3. a kind of device in high strength steel surface continuous vacuum evaporation metal antimony as described in claim 1, it is characterised in that:
Tongue uses square structure, is highly 50~70 ㎝, width is 5~10 ㎝ bigger than the high strength steel board width of required vapor deposition.
4. a kind of device in high strength steel surface continuous vacuum evaporation metal antimony as described in claim 1, it is characterised in that:
Tongue mouth uses square structure, is highly 5~10 ㎝, width is consistent with tongue.
5. a kind of device in high strength steel surface continuous vacuum evaporation metal antimony as described in claim 1, it is characterised in that:
High-strength steel sheet is 15 ㎝ at a distance from tongue with holes.
6. utilizing device as described in claim 1 in the method for high strength steel surface continuous vacuum evaporation metal antimony, feature exists
In:
(1) the adsorbent Zr-16Al of vaporization chamber wall outer side is preheated 3 hours at 800 DEG C using adsorbent heater, removal
Active gases in vacuum chamber, steel plate and antimony regulus are in room temperature at this time, after the completion of absorption, stop the heating of adsorbent;
(2) it utilizes evaporation heater by evaporation source antimony regulus in 677 DEG C of continuous heatings, so that the heat preservation of substrate steel disc is existed around resistance band
230~300 DEG C;
(3) high-strength steel sheet slow transits through left and right sides tongue spray antimony mouth in three times from top to bottom, using antimony in 677 DEG C of corresponding steamings
Air pressure is 10-2Torr, the characteristic that evaporation effect is optimal and high temperature atomic can be moved to low temperature face are equal by the two-sided covering of high strength steel
Even antimony protective film;
(4) steel plate after the completion of cooling utilizes detection contact pilotage detection vapor deposition film thickness.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710881086.7A CN107723663B (en) | 2017-09-26 | 2017-09-26 | A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710881086.7A CN107723663B (en) | 2017-09-26 | 2017-09-26 | A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107723663A CN107723663A (en) | 2018-02-23 |
CN107723663B true CN107723663B (en) | 2019-11-12 |
Family
ID=61207998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710881086.7A Active CN107723663B (en) | 2017-09-26 | 2017-09-26 | A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107723663B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019239185A1 (en) * | 2018-06-13 | 2019-12-19 | Arcelormittal | Vacuum deposition facility and method for coating a substrate |
CN112505286B (en) * | 2019-09-16 | 2023-08-11 | 中国科学院上海光学精密机械研究所 | Detection device and method for zinc-induced liquid metal crack formation condition |
CN116024529A (en) * | 2021-10-27 | 2023-04-28 | 宝山钢铁股份有限公司 | Galvanized sheet production method and production line |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN2632980Y (en) * | 2003-07-16 | 2004-08-11 | 上海大学 | Vacuum evaporating heater for producing organic electroluminescent thin membrane |
JP2010245312A (en) * | 2009-04-07 | 2010-10-28 | Hitachi Cable Ltd | Light-emitting element |
KR20120116720A (en) * | 2011-04-13 | 2012-10-23 | 에스엔유 프리시젼 주식회사 | Apparatus for supplying materials |
KR101052435B1 (en) * | 2011-04-13 | 2011-07-28 | 에스엔유 프리시젼 주식회사 | Depositing apparatus for forming thin film |
CN103628025A (en) * | 2012-08-21 | 2014-03-12 | 深圳富泰宏精密工业有限公司 | Alloy coevaporation material and evaporation coating method employing alloy coevaporation material |
CN105112914A (en) * | 2015-08-31 | 2015-12-02 | 中国钢研科技集团有限公司 | Continuous hot-dip galvanizing device and continuous hot-dip galvanizing method |
-
2017
- 2017-09-26 CN CN201710881086.7A patent/CN107723663B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN107723663A (en) | 2018-02-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107723663B (en) | A kind of device and method in high strength steel surface continuous vacuum evaporation metal antimony | |
WO2008018308A1 (en) | Method for quenching of steel member, quenched steel member, and agent for protecting quenched surface | |
JP5799819B2 (en) | Method for producing hot-dip galvanized steel sheet with excellent plating wettability and pick-up resistance | |
CN105531389A (en) | Hot-dip galvanized steel sheet and galvannealed steel sheet of excellent appearance and plating adhesiveness, and manufacturing method therefor | |
JP6356808B2 (en) | Annealing method of steel sheet | |
CN105177573B (en) | The Unit erriger and its production method of continuous hot galvanizing of steel strip and plating zinc magnesium alloy | |
CN105531390A (en) | Hot-dip galvanized steel sheet and galvannealed steel sheet of excellent appearance and plating adhesiveness, and manufacturing method therefor | |
CN104379775A (en) | Automotive components formed of sheet metal coated with a non-metallic coating | |
CN105960480A (en) | Alloyed hot-dip galvanized steel sheet and method for producing same | |
CN102816986A (en) | Strip steel continuous hot galvanizing method | |
KR101707981B1 (en) | Method for manufacturing galvanized steel sheet | |
JP5488322B2 (en) | Steel plate manufacturing method | |
CN114032475A (en) | High-strength cold-rolled hot-galvanized medium manganese steel, preparation method thereof and hot-formed part | |
CN106011394A (en) | Heat treatment process adopting three-section type heating for metal workpiece | |
KR101126014B1 (en) | Manufacturing Method of Galvannealed Steel Sheet | |
US20160186330A1 (en) | Composition and coating structure applying with the same | |
CN107354424B (en) | A kind of vapor deposition zinc pretreating process inhibiting high-strength steel surface of steel plate selective oxidation | |
CN107000020A (en) | The manufacture method and hot press-formed article of hot press-formed article | |
CN102758162B (en) | Plating solution and plating method for aluminum alloy plated steel plate | |
WO2021125728A3 (en) | Grain-oriented electrical steel sheet and method for manufacturing same | |
CN105506509B (en) | A kind of high intensity aludip and its manufacture method | |
CN112813371B (en) | Method for galvanizing dual-phase steel | |
CN104651856A (en) | Carbonitriding heat treatment technology of bearing roller | |
CN102031474A (en) | Method for producing high-strength hot dipped galvanized steel strips | |
CN102051571A (en) | Superficial zone carburizing process for surface layer of steel piece |
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 |