CN112500832A - Preparation method of foam nickel-based oxide composite wave-absorbing material - Google Patents
Preparation method of foam nickel-based oxide composite wave-absorbing material Download PDFInfo
- Publication number
- CN112500832A CN112500832A CN202011452813.6A CN202011452813A CN112500832A CN 112500832 A CN112500832 A CN 112500832A CN 202011452813 A CN202011452813 A CN 202011452813A CN 112500832 A CN112500832 A CN 112500832A
- Authority
- CN
- China
- Prior art keywords
- absorbing material
- foam nickel
- wave
- based oxide
- composite wave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of inorganic wave-absorbing materials, and relates to a preparation method of a composite wave-absorbing material formed by in-situ growth of oxides on a foam nickel substrate by a solvent-free method, which comprises the following steps: s1, mixing the divalent nickel salt, the metal salt of the oxide to be generated and the low-melting-point polymer, grinding uniformly and drying to obtain a precursor; and S2, calcining the precursor to obtain the foam nickel-based oxide composite wave-absorbing material. The preparation method of the foam nickel-based oxide composite wave-absorbing material provided by the invention has the advantages of simple process, short preparation period, low requirement on production equipment and easiness in industrial production; the prepared foam nickel-based wave-absorbing material has the advantages of light weight, wide wave-absorbing frequency band and strong absorbing capacity.
Description
Technical Field
The invention relates to a preparation method for forming a composite wave-absorbing material by growing oxides on a foam nickel substrate in situ by a solvent-free method, belonging to the field of inorganic wave-absorbing materials.
Background
With the rapid development of the electronic industry, electronic devices such as computers and wireless communication devices have been widely popularized in the production and life of human beings. The electromagnetic wave radiated by the electronic equipment using the electromagnetic wave as the information carrier causes serious electromagnetic interference, and the performance of the precision electronic equipment is reduced or even broken down due to the electromagnetic wave interference. In addition, the heat effect generated after the electromagnetic wave enters the human body can cause harm to the health of the human body and simultaneously can cause diseases of a nervous system, an immune system and an endocrine system. Therefore, with the rapid development of modern high and new electronic technology and the improvement of attention paid to body health care, the requirements on various performances such as wave absorbing performance, heat resistance, corrosion resistance, density and the like of the wave absorbing material are higher and higher. Therefore, research and development of novel wave-absorbing materials have become the focus of extensive attention of researchers.
The wave-absorbing material must satisfy impedance matching characteristics and attenuation characteristics in order to achieve good absorption properties. The impedance matching characteristic means that incident electromagnetic waves can enter the wave-absorbing material to the maximum extent without being reflected on the surface of the wave-absorbing material, and the attenuation characteristic means that the electromagnetic waves entering the wave-absorbing material are lost to the maximum extent. The wave-absorbing material mainly realizes the absorption of electromagnetic waves through the mechanisms of dielectric loss and magnetic loss. Dielectric losses include interfacial polarization losses, dipole polarization losses, conductance losses, and magnetic losses include natural resonance, exchange resonance, and eddy current losses. For the wave-absorbing material with a single loss mechanism, the requirements of impedance matching and attenuation characteristics cannot be met simultaneously. Therefore, the prepared novel wave-absorbing material needs to have multiple loss mechanisms simultaneously, so that the requirements of light thickness, thin mass, wide absorption frequency band and strong absorption capacity are met.
The light metal foam nickel material with multiple pore channels realizes light and multifunctional material, and can provide strong magnetic loss and electric conduction loss due to strong magnetism and electric conductivity, thereby showing a certain application prospect in the field of wave absorption. However, the single-component nickel foam material cannot achieve effective absorption because of the reflection of electromagnetic waves on the surface due to the high conductivity of the single-component nickel foam material. Therefore, nickel foam-based wave-absorbing materials have been reported. In order to meet the requirements of 'thin, light, wide and strong' of the absorbing material, oxide materials are required to be loaded on the foamed nickel to meet the requirements. The advantages of supported oxides are manifested in two ways: 1. the better impedance matching characteristic is provided, so that the electromagnetic waves can enter the wave-absorbing material more easily and are lost; 2. the interface polarization effect is enhanced, the formation of a foam nickel/oxide interface is caused due to the generation of the oxide, and the interface polarization effect is generated on a two-phase interface due to the different performances of different materials, so that the wave absorbing capacity is enhanced. However, the research process of loading oxide on the currently reported nickel foam is very complicated, and the complex pretreatment of commercial nickel foam is often needed, and then the oxide is grown on the nickel foam by using a chemical means, and the complex processes not only prolong the preparation period of the material, but also need to spend higher cost, thereby greatly limiting the practical application thereof. CN105023768B, CN103359796A, CN104925790B, CN104332328B and the like respectively disclose preparation methods of the composite material with oxide loaded on the foamed nickel, but the disclosed methods all have the problems of complicated preparation process, high cost and the like.
Disclosure of Invention
The invention provides a method for quickly, simply and conveniently preparing a foam nickel-based oxide composite wave-absorbing material by a solvent-free method, which has the advantages of simple process, short preparation period, low requirement on production equipment and easy industrial production; the prepared foam nickel-based wave-absorbing material has the advantages of light weight, wide wave-absorbing frequency band and strong absorbing capacity.
The preparation method of the foam nickel-based oxide composite wave-absorbing material provided by the invention comprises the following steps of:
s1, mixing the divalent nickel salt, the metal salt of the oxide to be generated and the low-melting-point polymer, grinding uniformly and drying to obtain a precursor;
the positive ions of the metal salt of the oxide to be generated are one of cobalt ions, iron ions, copper ions and zinc ions, and the negative ions are one of chloride ions, nitrate radicals, acetate radicals and sulfate radicals;
the molar ratio of the metal salt of the oxide to be generated to the divalent nickel salt is 0.1-0.5: 1;
the low-melting-point polymer is a polymer with a melting point of 50-60 ℃;
s2, calcining the precursor at the temperature of 200-500 ℃ to obtain the foam nickel-based oxide composite wave-absorbing material.
Preferably, the anion of the divalent nickel salt is one of chloride, nitrate, acetate and sulfate.
Preferably, the low melting polymer is F127 or P123, or a mixture of both.
Preferably, the molar ratio of the low melting point polymer to the divalent nickel salt is 0.0016-0.04: 1.
Preferably, the drying is at 60-100 ℃ for 3-12 h.
Preferably, the calcination is performed for 30min-3h after the temperature is raised to 200-500 ℃ at the temperature raising rate of 1-10 ℃/min.
Preferably, the grinding time is 10min to 20 min.
The invention also provides a foam nickel-based oxide composite wave-absorbing material prepared by the preparation method, which is of a light porous structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional complex pretreatment of loading the oxide on the commercial foam nickel and the high-energy-consumption hydrothermal reaction growth method, the method disclosed by the invention has the advantages that the loading step of the target oxide on the foam nickel is completed simultaneously in the process of forming the self-made foam nickel by using the in-situ growth method, so that the experimental steps are simplified;
(2) the preparation process is simple, the time consumption is short, and the repeatability and the controllability are strong;
(3) the density of the material is extremely low and is about 0.06g/cm3The requirement of light wave-absorbing material is met, the effective absorption frequency band is wide, and the requirement of wide wave-absorbing material is met;
(4) the adopted raw materials are cheap and easy to obtain, and the method has industrialization potential.
Drawings
FIG. 1 is an X-ray diffraction pattern of a wave-absorbing material; wherein, S1, S2 and S3 represent examples 1, 2 and 3, respectively;
FIG. 2 is a scanning electron microscope image of the wave-absorbing material prepared in example 1;
FIG. 3 is a wave-absorbing property diagram of the wave-absorbing material prepared in example 1;
FIG. 4 is a scanning electron microscope image of the wave-absorbing material prepared in example 2;
FIG. 5 is a scanning electron microscope image of the wave-absorbing material prepared in example 3;
FIG. 6 is an X-ray diffraction pattern of a wave-absorbing material prepared when the mass ratio of copper nitrate to nickel nitrate is less than 0.1;
FIG. 7 is a scanning electron microscope image of the wave-absorbing material prepared when the ratio of the amount of cobalt nitrate to the amount of nickel nitrate is greater than 0.5.
Detailed Description
The present invention is further described below by way of examples, but the present invention is not limited by these examples. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
According to the ratio of the amount of the metallic nickel source to the amount of the oxide metal salt to be grown, 1: 0.3 accurately weigh 1.45g of Ni (NO)3)2·6H2O and 0.4054g FeCl3·6H2Placing O and 1gF127 in an agate mortar, and grinding for 10min until the materials are uniformly mixed; collecting the uniformly mixed materials, and drying the materials in a forced air drying oven at 80 ℃ for 6h to obtain a foaming material precursor; and finally calcining for 2h at 500 ℃ at the heating rate of 3 ℃/min to obtain the nickel ferrite loaded foam nickel-based oxide composite wave-absorbing material.
In FIG. 1, S1 is the X-ray diffraction pattern of the prepared sample. The main peak is the peak of the metal nickel, the diffraction peak of the nickel ferrite can be observed by amplifying the spectrogram, the peak type is good, and the crystallinity is good.
Fig. 2 is a scanning electron microscope image of the synthetic wave-absorbing material of this embodiment, and it can be seen from the image that the material is in a regular porous state.
Example 2
According to the mass ratio of 1: 0.1 accurately weigh 1.45gNi (NO)3)2·6H2O and 0.1488g Zn (NO)3)2·6H2O and 0.5g of P123, placing in an agate mortar, and grinding for 15min until the materials are mixed uniformly. Collecting the mixed materials, and drying at 60 deg.C for 12 hr in a forced air drying oven to obtainA foam material precursor. And finally calcining for 3h at 200 ℃ at the heating rate of 1 ℃/min to obtain the zinc oxide loaded foam nickel-based oxide composite wave-absorbing material.
In FIG. 1, S2 is the X-ray diffraction pattern of the prepared sample.
Fig. 4 is a scanning electron microscope image of the wave-absorbing material prepared in this embodiment, and it can be seen from the image that the porous zinc oxide-loaded porous foam nickel-based material is obtained.
Example 3
According to the mass ratio of 1: 0.5 accurately weigh 1.45gNi (NO)3)2·6H2O and 0.5948g CoCl2·6H2O and 0.5gF127, placing in an agate mortar, and grinding for 20min until the materials are mixed uniformly. And collecting the uniformly mixed materials, and drying the materials in a forced air drying oven at 100 ℃ for 3h to obtain a foaming material precursor. And finally calcining the mixture at 400 ℃ for 30min at the temperature rise rate of 10 ℃/min to obtain the nickel oxide-loaded foam nickel-based oxide composite wave-absorbing material.
In FIG. 1, S3 is the X-ray diffraction pattern of the prepared sample.
Fig. 5 is a scanning electron microscope image of the wave-absorbing material prepared in this embodiment, and it can be seen from the image that the nickel oxide-loaded porous foam nickel-based material shows a regular morphology.
In the preparation process of the foam nickel-based oxide composite wave-absorbing material, the addition amount of corresponding metal salt of the foam nickel-based oxide composite wave-absorbing material needs to be strictly controlled according to the type of the oxide to be generated, when the addition amount is insufficient, a target oxide cannot be generated on foam nickel in situ, for example, for the addition of copper nitrate, when the ratio of the addition amount to the amount of nickel nitrate is less than 0.1, oxide load cannot be obtained, and particularly, see fig. 6; if the addition amount is excessive, the three-dimensional network structure of the foam nickel connected can be damaged, and the foam nickel-based oxide composite material with a regular morphology cannot be obtained, for example, for the addition of cobalt nitrate, when the ratio of the addition amount to the amount of nickel nitrate is greater than 0.5, a discontinuous material with a product morphology showing fracture is obtained, as shown in fig. 7.
Since the wave absorbing properties of the foam nickel-based oxide composite materials prepared in the embodiments 1 to 3 are substantially the same, the wave absorbing properties of the prepared foam nickel-based nickel ferrite composite wave absorbing material are tested by using a vector network analyzer (VNA, Anritsu MS46322B, Japan) by taking the embodiment 1 as an example, and the results are shown in FIG. 3.
As can be seen from FIG. 3, in the 2-18GHz test range, the absorption peak of the reflection loss shifts to a low frequency as the thickness of the test sample increases. At 16.8GHz, the reflection loss peak value of a composite material sample with the thickness of 2.1mm is-49.95 dB, the effective bandwidth of RL < -10dB is 8.88GHz (8.48-17.36GHz), and the electromagnetic wave of the frequency band can be effectively absorbed.
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (8)
1. A preparation method of a foam nickel-based oxide composite wave-absorbing material is characterized by comprising the following steps:
s1, mixing the divalent nickel salt, the metal salt of the oxide to be generated and the low-melting-point polymer, grinding uniformly and drying to obtain a precursor;
the positive ions of the metal salt of the oxide to be generated are one of cobalt ions, iron ions, copper ions and zinc ions, and the negative ions are one of chloride ions, nitrate radicals, acetate radicals and sulfate radicals;
the molar ratio of the metal salt of the oxide to be generated to the divalent nickel salt is 0.1-0.5: 1;
the low-melting-point polymer is a polymer with a melting point of 50-60 ℃;
s2, calcining the precursor at the temperature of 200-500 ℃ to obtain the foam nickel-based oxide composite wave-absorbing material.
2. The method for preparing the foam nickel-based oxide composite wave-absorbing material as claimed in claim 1, wherein the anion of the divalent nickel salt is one of chloride, nitrate, acetate and sulfate.
3. The method for preparing the foam nickel-based oxide composite wave-absorbing material as claimed in claim 1, wherein the low-melting polymer is F127 or P123, or a mixture of the two.
4. The preparation method of the foam nickel-based oxide composite wave-absorbing material as claimed in claim 3, wherein the molar ratio of the low-melting-point polymer to the divalent nickel salt is 0.0016-0.04: 1.
5. The preparation method of the foam nickel-based oxide composite wave-absorbing material according to claim 1, wherein the drying is performed at 60-100 ℃ for 3-12 h.
6. The method for preparing the foam nickel-based oxide composite wave-absorbing material as claimed in claim 1, wherein the calcination is performed for 30min-3h after the temperature is raised to 200-500 ℃ at a temperature raising rate of 1-10 ℃/min.
7. The preparation method of the foam nickel-based oxide composite wave-absorbing material according to claim 1, wherein the grinding time is 10min to 20 min.
8. The foam nickel-based oxide composite wave-absorbing material prepared according to any one of claims 1 to 7, characterized in that the foam nickel-based oxide composite wave-absorbing material is of a lightweight porous structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452813.6A CN112500832B (en) | 2020-12-11 | 2020-12-11 | Preparation method of foam nickel-based oxide composite wave-absorbing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452813.6A CN112500832B (en) | 2020-12-11 | 2020-12-11 | Preparation method of foam nickel-based oxide composite wave-absorbing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112500832A true CN112500832A (en) | 2021-03-16 |
| CN112500832B CN112500832B (en) | 2023-04-18 |
Family
ID=74973140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011452813.6A Active CN112500832B (en) | 2020-12-11 | 2020-12-11 | Preparation method of foam nickel-based oxide composite wave-absorbing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112500832B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875391A (en) * | 2022-04-21 | 2022-08-09 | 南京信息工程大学 | Preparation method of FeCo alloy coated foam nickel wave-absorbing material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100877280B1 (en) * | 2007-08-24 | 2009-01-07 | 주식회사 에코세라 | Cellular glass block absorbable electromagnetic wave on wide range and manufacturing process of the same |
| CN101819842A (en) * | 2009-12-16 | 2010-09-01 | 南京航空航天大学 | Method for preparing C-SiO2-Fe/M magnetic mesoporous composite material for electromagnetic wave adsorption coating |
| US8415568B1 (en) * | 2009-02-02 | 2013-04-09 | Conductive Composites Company, L.L.C. | Electromagnetic shielding |
| CN109705808A (en) * | 2019-02-02 | 2019-05-03 | 南京航空航天大学 | A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof |
| CN110461137A (en) * | 2019-07-31 | 2019-11-15 | 西北工业大学 | A kind of three-dimensional foam type composite wave-suction material and preparation method thereof |
| CN110790316A (en) * | 2019-10-21 | 2020-02-14 | 山东科技大学 | Iron oxide-nitrogen doped carbon micron tube composite wave-absorbing material and preparation method thereof |
-
2020
- 2020-12-11 CN CN202011452813.6A patent/CN112500832B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100877280B1 (en) * | 2007-08-24 | 2009-01-07 | 주식회사 에코세라 | Cellular glass block absorbable electromagnetic wave on wide range and manufacturing process of the same |
| US8415568B1 (en) * | 2009-02-02 | 2013-04-09 | Conductive Composites Company, L.L.C. | Electromagnetic shielding |
| CN101819842A (en) * | 2009-12-16 | 2010-09-01 | 南京航空航天大学 | Method for preparing C-SiO2-Fe/M magnetic mesoporous composite material for electromagnetic wave adsorption coating |
| CN109705808A (en) * | 2019-02-02 | 2019-05-03 | 南京航空航天大学 | A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof |
| CN110461137A (en) * | 2019-07-31 | 2019-11-15 | 西北工业大学 | A kind of three-dimensional foam type composite wave-suction material and preparation method thereof |
| CN110790316A (en) * | 2019-10-21 | 2020-02-14 | 山东科技大学 | Iron oxide-nitrogen doped carbon micron tube composite wave-absorbing material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QIN, M ET AL.: "\"Filter paper templated one-dimensional NiO/NiCo2O4 microrod with wideband electromagnetic wave absorption capacity\"" * |
| WEN, B ET AL.: "\"In situ anchoring carbon nanotubes on the Ni/C nanosheets with controllable thickness for boosting the electromagnetic waves absorption\"" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875391A (en) * | 2022-04-21 | 2022-08-09 | 南京信息工程大学 | Preparation method of FeCo alloy coated foam nickel wave-absorbing material |
| CN114875391B (en) * | 2022-04-21 | 2023-04-25 | 南京信息工程大学 | Preparation method of FeCo alloy coated foam nickel wave-absorbing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112500832B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705808B (en) | Cobalt-nickel alloy-porous carbon composite wave-absorbing material with MOF structure and preparation method thereof | |
| CN112961650B (en) | Three-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof | |
| CN108154984B (en) | Porous ferroferric oxide/carbon nano rod-shaped electromagnetic wave absorption material and preparation method and application thereof | |
| CN110591642B (en) | Preparation method of composite wave-absorbing material based on magnetic nanoparticles/graphene/carbon fibers | |
| CN111410194B (en) | Composite electromagnetic wave-absorbing foam prepared from ZIF-67/melamine and preparation method thereof | |
| CN112980390B (en) | Preparation method of bimetal organic framework derived magnetic carbon composite wave-absorbing material | |
| CN113088252A (en) | Iron-cobalt-nickel alloy/carbon/graphene ultrathin wave-absorbing material and preparation method thereof | |
| CN102745982B (en) | Method for preparing nanometer arsenic trioxide (ATO)/nanometer ferrite composite wave absorbing material | |
| CN109896520A (en) | A kind of magnetizing reduction stannic oxide/graphene nano composite material and preparation method and application | |
| CN111484080B (en) | Neodymium-doped praseodymium manganese oxide wave-absorbing powder material and preparation method thereof | |
| CN112500832B (en) | Preparation method of foam nickel-based oxide composite wave-absorbing material | |
| CN113840529A (en) | NiCo2O4@ agaric carbon aerogel composite material and preparation method and application thereof | |
| CN110461137B (en) | Three-dimensional foam type composite wave-absorbing material and preparation method thereof | |
| CN113816620B (en) | Dielectric fiber composite wave-absorbing material coated with molybdenum disulfide/iron-cobalt alloy/carbon on surface and preparation method thereof | |
| CN102153338A (en) | Seepage type barium titanate-nickel zinc ferrite composite ceramic wave absorption material and preparation method thereof | |
| CN114845538A (en) | Magnetic metal @ carbon composite wave-absorbing material derived from layered double-magnetic metal hydroxide and preparation method thereof | |
| CN114501966A (en) | Wave-absorbing material with zero-dimension/one-dimension/two-dimension composite nanostructure and preparation method and application thereof | |
| CN114073919B (en) | Carbon-magnetic metal dispersion type hollow composite microsphere and preparation method and application thereof | |
| CN112280533B (en) | Preparation method of ternary composite wave-absorbing material with hollow structure | |
| CN114956192A (en) | Lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and preparation method thereof | |
| CN110950320B (en) | Light hollow carbon cube wave-absorbing material and preparation method thereof | |
| CN110564365B (en) | Preparation method of graphene foam composite material loaded with magnetic hollow nanospheres | |
| CN115386339B (en) | Hollow echinoid cobalt-based sulfide composite wave-absorbing material and preparation method thereof | |
| CN115920790B (en) | Preparation method of multifunctional nitrogen-doped carbon aerogel | |
| CN115666117A (en) | Broadband three-dimensional dendritic wave-absorbing material 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 |