CN114149595B - High-elasticity hydrogel sensor and preparation method thereof - Google Patents
High-elasticity hydrogel sensor and preparation method thereof Download PDFInfo
- Publication number
- CN114149595B CN114149595B CN202111340087.3A CN202111340087A CN114149595B CN 114149595 B CN114149595 B CN 114149595B CN 202111340087 A CN202111340087 A CN 202111340087A CN 114149595 B CN114149595 B CN 114149595B
- Authority
- CN
- China
- Prior art keywords
- solution
- monomer
- mass
- accounts
- initiator
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
Abstract
The invention discloses a high-elasticity hydrogel sensor and a preparation method thereof. The double-network hydrogel sensor with the interpenetrating structure is prepared by adopting a one-step method, has high elasticity, and can accurately and effectively sense the size, shape and position of the force.
Description
Technical Field
The invention relates to a preparation method of a sensor, in particular to a high-elasticity hydrogel sensor and a preparation method thereof.
Background
The traditional sensor can only sense tiny deformation and cannot meet the requirements of large mechanical deformation such as bending, folding, twisting and stretching. Hydrogel sensors have good flexibility, ductility, and biocompatibility that can overcome the inherent stiffness of conventional sensors made from metallic or semiconductor materials. Therefore, the hydrogel sensor has wide application prospects in the fields of remote health monitoring, body movement tracking, electronic skin, wearable electronic equipment, soft robots and the like.
However, the existing hydrogel has poor mechanical properties, can be broken under low strain, and cannot be repaired and rebounded by itself. The preparation of the hydrogel with good mechanical properties has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a high-elasticity hydrogel sensor with excellent mechanical properties.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-elasticity hydrogel sensor comprises the following steps:
step 1, adding a first monomer into water, and uniformly stirring at 45-55 ℃ to obtain a solution A;
step 2, adding conductive filler into the solution A, and uniformly mixing at normal temperature to obtain a solution B;
step 3, adding a second monomer into the solution B, and uniformly mixing at normal temperature to obtain a solution C;
step 4, adding an initiator, a crosslinking agent and a catalyst into the solution C, and uniformly mixing at normal temperature to obtain a solution D;
and 5, pouring the solution D into a sealing mould, and placing the sealing mould into a baking oven at 35-65 ℃ for heat preservation and solidification for 3-6 hours to obtain the high-elasticity hydrogel sensor.
Further: let the total mass of the first monomer, the second monomer, the conductive filler, the initiator, the cross-linking agent and the catalyst be M, then: the mass of the first monomer is 5-20% of that of M, the mass of the second monomer is 56.8-91.35% of that of M, the mass of the conductive filler is 0.1-5% of that of M, the mass of the initiator is 0.5-2% of that of M, the mass of the cross-linking agent is 0.05-0.2% of that of M, and the mass of the catalyst is 3-16% of that of M.
Further, in the solution D, the mass percentage of water is 75% -95%.
Further, the first monomer is one of sodium alginate, chitosan, gelatin (Gelatin), carrageenan and kadlan.
Further, the second monomer is one of acrylamide, acrylic acid, isopropyl acrylamide and acrylamide methyl propane sulfonic acid.
Further, the conductive filler is at least one of lithium chloride, calcium chloride, ferric dichloride, sodium chloride, sodium sulfate, aluminum chloride, polypyrrole, polyaniline, liquid metal, carbon black, graphene oxide and carbon nanotubes.
Further, the initiator is one of ammonium persulfate and potassium persulfate.
Further, the cross-linking agent is one of methylene dipropylamide, polyethylene glycol methyl methacrylate and cetyl methacrylate.
Further, the catalyst is one of tetramethyl ethylenediamine and cetyl trimethyl ammonium bromide.
Compared with the prior art, the invention has the beneficial effects that:
1. when the hydrogel sensor is prepared, the first monomer and the second monomer are crosslinked in two modes of physical crosslinking and chemical crosslinking respectively, the physical crosslinking forms a first network, the chemical crosslinking forms a second network, and the two network structures are interpenetrating, so that a good synergistic effect is achieved. The independent chemical crosslinking structure has better strength, but can not be repaired by itself after being damaged by stress; the individual physical crosslinking structure has good elasticity and can be repaired by itself after being damaged by stress. The invention complements the two structures to obtain the double-network high-elasticity hydrogel with an interpenetrating structure.
2. The invention obtains the hydrogel with good mechanical property, in particular to the elastic property. After the deformation is impacted by external force, the deformation can be quickly recovered after the external force is removed, and the attenuation of the stress after 20 times of repeated compression is less than or equal to 25 percent.
3. The hydrogel sensor can rapidly and accurately sense the magnitude, shape and position of force, and the response time is 5 s-10 s.
4. The inorganic salt is added as the conductive filler in the preparation process of the hydrogel, so that the inorganic salt can effectively prevent the water loss of the hydrogel sensor, and the application range and the application conditions of the hydrogel sensor are further enlarged.
5. The preparation process of the hydrogel is simple, and the hydrogel is easy to popularize in a large range.
Drawings
FIG. 1 is a stress strain diagram of the high elasticity hydrogel sensor prepared in example 1 repeatedly compressed 20 times;
FIG. 2 shows the response of the high elasticity hydrogel sensor prepared in example 1 to the magnitude, shape and position of force.
Detailed Description
To further illustrate the features and advantages of the present invention, the following detailed description of embodiments of the present invention is provided as part of the present invention, and the scope of the present invention is not limited to the following embodiments.
Reagents, materials, and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The high elasticity hydrogel sensor was prepared as follows:
(1) 20g of Gelatin was added to 400mL of deionized water and stirred at 50℃for 30min to obtain solution A.
(2) Adding 4.8g of liquid gallium indium tin metal and 0.2g of short-wall carbon nano tube into the solution A, firstly using ultrasonic oscillation for 5min, and then stirring and mixing at normal temperature for 30min to obtain a solution B.
(3) 56.8g of isopropyl acrylamide is added into the solution B, and the mixture is stirred uniformly at normal temperature to obtain a solution C.
(4) 16g of tetramethyl ethylenediamine, 0.2g of methylenedipropylamide and 2g of potassium persulfate were sequentially added to the solution C and stirred uniformly at room temperature to obtain a solution D.
(5) Pouring the solution D into a sealing mould, putting into a 60 ℃ oven for heat preservation and solidification for 5 hours, taking out, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
FIG. 1 is a stress strain diagram of the high elasticity hydrogel sensor prepared in this example, which is repeated 20 times, and it can be seen from the diagram that the hydrogel rapidly rebounds when the pressure is removed.
The hydrogel sensors of 20cm x 20cm prepared in this example are shown on the right side of fig. 2, and the computer on the left side collects data and images. And preparing a silica gel mold with the length and the width of 20cm respectively in advance, and embedding 16 electrodes in the mold. Pouring the prepared solution D into a silica gel mold, sealing the solution by using a preservative film, and putting the solution D into an oven for curing to obtain the hydrogel sensor. As can be seen from fig. 2, the sensor is pressed with a plastic cylinder, which allows a clear image.
Example 2
The high elasticity hydrogel sensor was prepared as follows:
(1) 5g of Gelatin was added to 400mL of deionized water and stirred at 50℃for 30min to obtain solution A.
(2) 0.1g of ferric trichloride is added into the solution A, and the mixture is stirred at normal temperature for 20min to obtain a solution B.
(3) 91.35g of acrylamide was added to the solution B and stirred uniformly at room temperature to obtain a solution C.
(4) 3g of tetramethyl ethylenediamine, 0.05g of methylenedipropylamide and 0.5g of potassium persulfate were sequentially added to the solution C and stirred uniformly at room temperature to obtain a solution D.
(5) Pouring the solution D into a sealing mould, putting into a 60 ℃ oven for heat preservation and solidification for 5 hours, taking out, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
The test shows that the hydrogel obtained by the embodiment has good mechanical properties, especially elastic properties.
Example 3
The high elasticity hydrogel sensor was prepared as follows:
(1) 8.42g of sodium alginate was added to 400mL of deionized water and stirred at 45℃for 20min to give solution A.
(2) 1.754g of ferric trichloride and 0.35g of graphene oxide are added into the solution A, ultrasonic vibration is firstly used for 5min, and stirring and mixing are carried out at normal temperature for 30min, so as to obtain a solution B.
(3) 23.9128g of acrylic acid was added to the solution B and stirred uniformly at room temperature to obtain a solution C.
(4) 6.736g of cetyltrimethylammonium bromide, 0.0842g of methylenedipropylamide and 0.842g of ammonium persulfate were added to the solution C in this order and stirred uniformly at room temperature to obtain a solution D.
(5) Pouring the solution D into a sealing mould, putting into a 55 ℃ oven for heat preservation and solidification for 4 hours, taking out, and naturally cooling to room temperature to obtain the high-elasticity hydrogel sensor.
The test shows that the hydrogel obtained by the embodiment has good mechanical properties, especially elastic properties.
The foregoing is illustrative only and is not intended to limit the present invention, and any modifications, equivalents, improvements and modifications falling within the spirit and principles of the invention are intended to be included within the scope of the present invention.
Claims (6)
1. The preparation method of the high-elasticity hydrogel sensor is characterized by comprising the following steps of:
step 1, adding a first monomer into water, and uniformly stirring at 45-55 ℃ to obtain a solution A;
step 2, adding conductive filler into the solution A, and uniformly mixing at normal temperature to obtain a solution B;
step 3, adding a second monomer into the solution B, and uniformly mixing at normal temperature to obtain a solution C;
step 4, adding an initiator, a crosslinking agent and a catalyst into the solution C, and uniformly mixing at normal temperature to obtain a solution D;
pouring the solution D into a sealing mould, and placing the sealing mould into a baking oven at 35-65 ℃ for heat preservation and solidification for 3-6 hours to obtain the high-elasticity hydrogel sensor;
let the total mass of the first monomer, the second monomer, the conductive filler, the initiator, the cross-linking agent and the catalyst be M, then: the mass of the first monomer accounts for 5-20% of that of M, the mass of the second monomer accounts for 56.8-91.35% of that of M, the mass of the conductive filler accounts for 0.1-5% of that of M, the mass of the initiator accounts for 0.5-2% of that of M, the mass of the cross-linking agent accounts for 0.05-0.2% of that of M, and the mass of the catalyst accounts for 3-16% of that of M;
the first monomer is one of sodium alginate, chitosan, gelatin, carrageenan and carrageenan; the second monomer is one of acrylamide, acrylic acid, isopropyl acrylamide and acrylamide methyl propane sulfonic acid; the conductive filler is at least one of lithium chloride, calcium chloride, ferric dichloride, sodium chloride, sodium sulfate, aluminum chloride, polypyrrole, polyaniline, liquid metal, carbon black, graphene oxide and carbon nanotubes.
2. The method of manufacturing according to claim 1, characterized in that: in the solution D, the mass percentage of water is 75-95%.
3. The method of manufacturing according to claim 1, characterized in that: the initiator is one of ammonium persulfate and potassium persulfate.
4. The method of manufacturing according to claim 1, characterized in that: the cross-linking agent is one of methylene dipropylamide, polyethylene glycol methyl methacrylate and cetyl methacrylate.
5. The method of manufacturing according to claim 1, characterized in that: the catalyst is one of tetramethyl ethylenediamine and cetyl trimethyl ammonium bromide.
6. A highly elastic hydrogel sensor obtained by the method according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340087.3A CN114149595B (en) | 2021-11-12 | 2021-11-12 | High-elasticity hydrogel sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111340087.3A CN114149595B (en) | 2021-11-12 | 2021-11-12 | High-elasticity hydrogel sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114149595A CN114149595A (en) | 2022-03-08 |
| CN114149595B true CN114149595B (en) | 2023-05-02 |
Family
ID=80460230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111340087.3A Active CN114149595B (en) | 2021-11-12 | 2021-11-12 | High-elasticity hydrogel sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149595B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004031253A1 (en) * | 2002-10-02 | 2004-04-15 | Coloplast A/S | A hydrogel |
| CN105175755A (en) * | 2015-08-27 | 2015-12-23 | 华南理工大学 | High-strength and high-tensile double-network physical cross-linking hydrogel and preparation method therefor |
| CN107805308A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
| CN110540658A (en) * | 2019-08-08 | 2019-12-06 | 天津大学 | acrylamide/carbon oxide nanotube-based nanocomposite hydrogel sensor and preparation method thereof |
| CN111269439A (en) * | 2020-01-07 | 2020-06-12 | 湖北大学 | Chitosan/poly (acrylamide-acrylic acid) -Al3+Ionic hydrogel and preparation method and application thereof |
| CN112724339A (en) * | 2021-04-06 | 2021-04-30 | 湖南大学 | Hydrogel flexible strain sensor and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8821583B2 (en) * | 2004-10-05 | 2014-09-02 | The Board Of Trustees Of The Leland Stanford Junior University | Interpenetrating polymer network hydrogel |
-
2021
- 2021-11-12 CN CN202111340087.3A patent/CN114149595B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004031253A1 (en) * | 2002-10-02 | 2004-04-15 | Coloplast A/S | A hydrogel |
| CN105175755A (en) * | 2015-08-27 | 2015-12-23 | 华南理工大学 | High-strength and high-tensile double-network physical cross-linking hydrogel and preparation method therefor |
| CN107805308A (en) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | A kind of dynamic aggregation thing and its application with hybrid cross-linked network |
| CN110540658A (en) * | 2019-08-08 | 2019-12-06 | 天津大学 | acrylamide/carbon oxide nanotube-based nanocomposite hydrogel sensor and preparation method thereof |
| CN111269439A (en) * | 2020-01-07 | 2020-06-12 | 湖北大学 | Chitosan/poly (acrylamide-acrylic acid) -Al3+Ionic hydrogel and preparation method and application thereof |
| CN112724339A (en) * | 2021-04-06 | 2021-04-30 | 湖南大学 | Hydrogel flexible strain sensor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 庞相琛 ; .自愈合水凝胶的应用研究进展.价值工程.2020,(01),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149595A (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fu et al. | A self-healing, recyclable and conductive gelatin/nanofibrillated cellulose/Fe 3+ hydrogel based on multi-dynamic interactions for a multifunctional strain sensor | |
| CN112500585B (en) | CS/TA/PAA-Al3+ composite ionic hydrogel and preparation method and application thereof | |
| CN107840971A (en) | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof | |
| Ma et al. | Ultra-sensitive, durable and stretchable ionic skins with biomimetic micronanostructures for multi-signal detection, high-precision motion monitoring, and underwater sensing | |
| Wei et al. | Water‐Resistant Conductive Gels toward Underwater Wearable Sensing | |
| CN111234112A (en) | Hydrogel flexible strain sensor and preparation method thereof | |
| Lei et al. | Environmentally Adaptive Polymer Hydrogels: Maintaining Wet‐Soft Features in Extreme Conditions | |
| CN112724339B (en) | Hydrogel flexible strain sensor and preparation method thereof | |
| Wang et al. | Highly stretchable, compressible, adhesive, conductive self-healing composite hydrogels with sensor capacity | |
| CN114149595B (en) | High-elasticity hydrogel sensor and preparation method thereof | |
| Liu et al. | Flexible strain sensors with rapid self-healing by multiple hydrogen bonds | |
| CN112979848B (en) | Liquid metal hydrogel and preparation method and application thereof | |
| CN111647111A (en) | Hydrogel electrolyte film with double-network structure and preparation method and application thereof | |
| Tang et al. | Graphene oxide composite hydrogels for wearable devices | |
| Zhou et al. | Dual-network polyvinyl alcohol/polyacrylamide/xanthan gum ionic conductive hydrogels for flexible electronic devices | |
| CN112679755A (en) | Preparation method of MXene-enhanced double-network self-healing conductive hydrogel | |
| Xia et al. | Recyclable hydrogel for human-machine interface of multi-mode human vital signal acquisition | |
| Sun et al. | Stretchable, self-healable and anti-freezing conductive hydrogel based on double network for strain sensors and arrays | |
| Zhao et al. | High-stretchable, self-healing, self-adhesive, self-extinguishing, low-temperature tolerant starch-based gel and its application in stimuli-responsiveness | |
| Zhang et al. | Mussel-inspired cellulose nanofiber/poly (vinyl alcohol) hydrogels with robustness, self-adhesion and antimicrobial activity for strain sensors | |
| He et al. | Temperature and pressure sensitive ionic conductive triple-network hydrogel for high-durability dual signal sensors | |
| Hang et al. | Highly stretchable polyvinyl alcohol composite conductive hydrogel sensors reinforced by cellulose nanofibrils and liquid metal for information transmission | |
| CN117106204A (en) | High-strength freeze-resistant conductive gel and preparation and application thereof | |
| CN112210114A (en) | Preparation method of ultrahigh-strength multifunctional polyvinyl alcohol-based oil gel elastomer | |
| CN114874463A (en) | Anti-freezing conductive hydrogel with excellent mechanical properties and preparation method and application thereof |
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 |