CN109616271B - Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof - Google Patents
Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof Download PDFInfo
- Publication number
- CN109616271B CN109616271B CN201811559048.0A CN201811559048A CN109616271B CN 109616271 B CN109616271 B CN 109616271B CN 201811559048 A CN201811559048 A CN 201811559048A CN 109616271 B CN109616271 B CN 109616271B
- Authority
- CN
- China
- Prior art keywords
- metal
- mnal
- doped
- magnetic refrigeration
- quartz tube
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C22/00—Alloys based on manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Hard Magnetic Materials (AREA)
Abstract
A Cu-doped MnAl-based magnetic refrigeration material and a preparation method thereof are disclosed, wherein the chemical general formula of the material is as follows: mnaAlbCucWherein a is 30-40, b is 50, c is 10-20, a + b + c is 100, and the Curie temperature of the material is 375-402K; the preparation method comprises the following steps: (1) preparing metal manganese, metal copper and metal aluminum; (2) putting the mixture into an electric arc melting furnace, repeatedly vacuumizing and introducing argon, and finally introducing argon to 0.3-0.8 standard atmospheric pressure; (3) starting an electric arc melting furnace for melting, and cooling along with the furnace; (4) after surface treatment, filling the quartz tube into the annealing furnace for annealing after vacuumizing the quartz tube; (5) taking out the quartz tube, quenching with water, and taking out the metal material. The preparation method disclosed by the invention is simple in preparation process, so that the application of the MnAl-based material in the field of magnetic refrigeration becomes possible, and zero breakthrough is realized.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a Cu-doped MnAl-based magnetic refrigeration material and a preparation method thereof.
Background
Magnetic refrigeration technology, as one of the most important technologies in the 21 st century, has the following advantages compared with the traditional refrigeration technology: 1. the magnetic refrigeration has higher refrigeration efficiency which can reach 30-60% of Carnot cycle, while the vapor compression refrigeration can only reach 5-10% of Carnot cycle; 2. because the magnetic entropy density of the magnetic material is far greater than that of the gas refrigerant, the volume of the refrigerating unit is smaller, and the operation is stable and reliable; 3. the noise is smaller, and the service life is longer; the core of the magnetic refrigeration is a magnetic field which is mainly provided by an electromagnet, a superconductor and a permanent magnet, so that the magnetic refrigeration does not need a compressor, and compared with the traditional refrigeration technology, the magnetic refrigeration has smaller noise and longer service life; 4. the most important point is that compared with various environmental problems brought by Freon compression refrigeration, the magnetic refrigeration technology is a high and new technology which is completely green and has no environmental pollution.
The main principle of the magnetic refrigeration technology is to utilize the magnetocaloric effect of the material, which is specifically shown in that the change of an external magnetic field can cause the change of the temperature of the material, so as to achieve the effect of refrigeration or heating; magnetic refrigeration technology is likely to replace traditional gas compression refrigeration in the future and becomes one of the most promising refrigeration technologies.
At present, materials researched by magnetic refrigeration generally contain rare earth elements, such as L aFeSi, GdSiGe and other rare earth magnetic refrigeration materials, and although the materials have very large magnetocaloric effect, the materials all contain the rare earth elements.
The MnAl material has a large amount of researches of researchers at home and abroad due to higher theoretical saturation magnetization (144emu/g), good machining performance, simple preparation process and low cost without containing rare earth elements, and the researches on the MnAl material are limited to the vigorous development of the hard magnetic performance of the MnAl material, such as the improvement of coercive force, magnetic energy product and other performances; the material has limited development in the field of magnetic refrigeration materials due to the large coercive force (4kOe) and the high Curie temperature (650K); at present, the application of MnAl materials in the field of magnetic refrigeration is still in a blank stage, so that the development of the MnAl-based soft magnetic material with near zero coercive force and low Curie temperature is significant.
Disclosure of Invention
The invention aims to provide a Cu-doped MnAl-based magnetic refrigeration material and a preparation method thereof, wherein the magnetic refrigeration material with the coercive force of less than 30Oe is prepared by introducing a copper element into a manganese-aluminum matrix and combining a smelting annealing process under the condition of not using rare earth.
The chemical general formula of the Cu-doped MnAl-based magnetic refrigeration material is as follows: mnaAlbCucWherein a is 30-40, b is 50, c is 10-20, and a + b + c is 100, and the Curie temperature is 375-402K.
Under the condition of a 0-1.5T magnetic field, the maximum magnetic entropy of the Cu-doped MnAl-based magnetic refrigeration material is 0.89-1.13J/kgK.
The Cu-doped MnAl-based magnetic refrigeration material is a soft magnetic material with the coercive force less than 30 Oe.
The preparation method of the Cu-doped MnAl-based magnetic refrigeration material comprises the following steps of:
1. preparing metal manganese, metal copper and metal aluminum, wherein the metal manganese is 30-40 parts by mass, the metal aluminum is 50 parts by mass and the metal copper is 10-20 parts by mass;
2. putting metal manganese, metal copper and metal aluminum into an electric arc melting furnace simultaneously; vacuumizing an electric arc melting furnace, introducing argon to normal pressure, and repeating the steps for three times; then vacuumizing, and finally introducing argon to 0.3-0.8 standard atmospheric pressure;
3. starting an electric arc melting furnace for melting, and cooling to normal temperature along with the furnace after melting to obtain an alloy ingot;
4. treating the surface of the alloy cast ingot to remove impurities, and then filling the alloy cast ingot into a quartz tube; vacuumizing the quartz tube, sealing, putting the quartz tube into an annealing furnace, and annealing for at least 72 hours at the temperature of 900 +/-10 ℃;
5. and after the annealing is finished, taking out the quartz tube, performing water quenching to normal temperature, and taking out the metal material from the quartz tube to obtain the Cu-doped MnAl-based magnetic refrigeration material.
The purities of the metal manganese, the metal copper and the metal aluminum are all more than or equal to 99.9 percent.
In the step 2, in order to compensate the volatilization of the manganese metal, the adding amount of the manganese metal is excessive by 3-6%.
In the step 2, the vacuum is pumped each time until the pressure in the electric arc melting furnace is less than or equal to 6 × 10-3Pa。
In the step 3, when smelting is carried out, the current is 100-200A; in order to ensure the uniformity of the alloy cast ingot, smelting is carried out for at least four times, the smelting time is 1-2 min each time, and the material is turned over after the previous smelting is finished and then is smelted for the next time.
In the step 4, the surface treatment is to polish the surface of the alloy cast ingot by using a grinder to be bright, then clean the surface by using alcohol, and then naturally air-dry the alloy cast ingot.
Compared with the traditional MnAl-based hard magnetic material, the product has extremely low coercive force, greatly reduced Curie temperature, low cost and excellent processing performance, and does not need to use rare earth elements; the preparation method disclosed by the invention is simple in preparation process, so that the application of the MnAl-based material in the field of magnetic refrigeration becomes possible, and zero breakthrough is realized.
Drawings
FIG. 1 shows the main phase Al of the Cu-doped MnAl-based magnetic refrigeration material of the invention5Cu2Mn3Schematic of the unit cell structure of the phase;
fig. 2 is a room temperature XRD pattern of Cu-doped MnAl-based magnetic refrigeration materials in example 1 and example 2 of the present invention; in the figure, the upper figure is embodiment 1, the lower figure is embodiment 2;
fig. 3 is a room temperature SEM image of Cu-doped MnAl-based magnetic refrigeration material in examples 1 and 2 of the present invention; in the figure, the right figure is embodiment 1, the left figure is embodiment 2;
FIG. 4 is a graph of the room temperature thermomagnetic curve (M-T) of a Cu-doped MnAl-based magnetic refrigerant material in examples 1 and 2 of the present invention, wherein ● is example 1, ■ is example 2;
FIG. 5 is a hysteresis loop diagram of a Cu-doped MnAl-based magnetic refrigeration material 300K in example 2 of the present invention;
FIG. 6 is an enlarged view of a portion of FIG. 5;
FIG. 7 is a hysteresis loop diagram of a Cu-doped MnAl-based magnetic refrigeration material 300K in example 1 of the present invention;
FIG. 8 is an enlarged view of a portion of FIG. 7;
FIG. 9 is a graph showing isothermal magnetization curves (M-H) of Cu-doped MnAl-based magnetic refrigerant material in example 2 of the present invention;
FIG. 10 is a graph showing isothermal magnetization curves (M-H) of Cu-doped MnAl-based magnetic refrigerant material in example 1 of the present invention;
FIG. 11 is a graph of magnetic entropy change versus temperature at different temperatures for a Cu-doped MnAl-based magnetic refrigeration material in example 2 of the present invention;
fig. 12 is a graph of magnetic entropy change versus temperature at different temperatures for the Cu-doped MnAl-based magnetic refrigeration material in example 1 of the present invention.
Detailed Description
In the Cu-doped MnAl-based magnetic refrigeration material in the embodiment of the invention, the main phase is mainly Al5Cu2Mn3A phase having a cubic Cs-Cl structure, wherein Al atoms occupy the apex position of the cell, Mn atoms and Cu atoms jointly occupy the core position of the cell, and the lattice constant is 2.97 angstroms, as shown in FIG. 1; part of the material has impurity phase Al8Mn5And (4) phase(s).
In the embodiment of the invention, the test equipment is an X-ray diffractometer with the model Smart L ab 9kW and a scanning electron microscope with the model JSM-7800F.
The apparatus for testing the magnetic properties of the materials in the examples of the present invention was the L AKESHORE vibrating sample magnetometer, USA.
In the embodiment of the invention, the formula for calculating the isothermal magnetic entropy change basis under different magnetic field conditions is as follows:
in the embodiment of the invention, the external magnetic field intensity is 0.1T when the test chamber is used for heating and magnetic performance.
The purity of the manganese metal, the copper metal and the aluminum metal adopted in the embodiment of the invention is more than or equal to 99.9 percent.
In the embodiment of the invention, the surface treatment is to polish the surface of the alloy cast ingot by using a grinder to be bright, then clean the surface by using alcohol, and then naturally dry the alloy cast ingot.
Example 1
Preparing 30 parts of metal manganese, 50 parts of metal aluminum and 20 parts of metal copper by mass;
putting metal manganese, metal copper and metal aluminum into an electric arc melting furnace simultaneously, in order to compensate the volatilization of the metal manganese, the adding amount of the metal manganese is excessive by 3 percent, firstly vacuumizing the electric arc melting furnace, then introducing argon to the normal pressure, repeatedly carrying out the steps for three times, then vacuumizing, finally introducing the argon to 0.8 standard atmospheric pressure, and vacuumizing each time until the pressure in the electric arc melting furnace is less than or equal to 6 × 10-3Pa；
Starting an electric arc melting furnace for melting, and cooling to normal temperature along with the furnace after melting to obtain an alloy ingot; when smelting is carried out, the current is 100-200A; in order to ensure the uniformity of the alloy cast ingot, four times of smelting are carried out, the time of each time of smelting is 2min, and the materials are turned over after the previous smelting is finished and then are smelted next time;
treating the surface of the alloy cast ingot to remove impurities, then filling the alloy cast ingot into a quartz tube, and sealing the quartz tube after vacuumizing; then placing the mixture into an annealing furnace, and annealing for 72 hours at the temperature of 900 +/-10 ℃;
after annealing, taking out the quartz tube, quenching the quartz tube to normal temperature, and taking out the metal material from the quartz tube to obtain the Cu-doped MnAl-based magnetic refrigeration material, wherein the chemical general formula of the Cu-doped MnAl-based magnetic refrigeration material is as follows: mn30Al50Cu20The Curie temperature is 375K; under the condition of a 0-1.5T magnetic field, the maximum magnetic entropy of the material is 0.89J/kgK; the material is coercive force<30Oe of a soft magnetic material;
the room temperature XRD pattern is shown in the upper graph of FIG. 2, the main phase is Al5Cu2Mn3The phase single-phase structure is shown in a room temperature SEM diagram of a right diagram of fig. 3, the structure has no miscellaneous structure, a room temperature thermomagnetic curve is shown in fig. 4, a hysteresis loop at 300K is shown in fig. 7 and fig. 8, the material has no hysteresis and thermal hysteresis, the coercive force at room temperature is less than 30Oe, the coercive force is greatly reduced compared with the traditional MnAl hard magnetic material, an isothermal magnetization curve is shown in fig. 10, and a magnetic entropy change-temperature curve at different temperatures is shown in fig. 12.
Example 2
The method is the same as example 1, except that:
(1) 40 parts of metal manganese, 50 parts of metal aluminum and 10 parts of metal copper in the metal manganese, the metal copper and the metal aluminum in parts by mass;
(2) in order to compensate the volatilization of the manganese metal, the addition amount of the manganese metal is excessive by 6 percent; vacuumizing the arc melting furnace, and introducing argon to 0.3 standard atmospheric pressure;
(3) five times of smelting are carried out to ensure the uniformity of the alloy cast ingot, and the smelting time is 1min each time;
(4) annealing at 900 +/-10 ℃ for 80 h;
(5) the chemical general formula of the Cu-doped MnAl-based magnetic refrigeration material is as follows: mnaAlbCucWherein a is 30-40, b is 50, c is 10-20, and a + b + c is 100, and the Curie temperature is 375-402K; the material is under the condition of 0-1.5T magnetic fieldThe maximum magnetic entropy becomes 0.89-1.13J/kgK; the material is coercive force<30Oe of a soft magnetic material;
the room temperature XRD pattern is shown in the lower graph of FIG. 2, the main phase is Al5Cu2Mn3Phase single phase structure, presence of hetero-phase Al8Mn5And the room temperature SEM image is shown in the left image of FIG. 3, the room temperature thermomagnetic curve is shown in FIG. 4, the hysteresis loop at 300K is shown in FIGS. 5 and 6, the material has no hysteresis and thermal hysteresis, the coercivity at room temperature is less than 30Oe, the coercivity is greatly reduced compared with the traditional MnAl hard magnetic material, the isothermal magnetization curve is shown in FIG. 9, and the magnetic entropy change-temperature curve at different temperatures is shown in FIG. 11.
Claims (3)
1. A preparation method of a Cu-doped MnAl-based magnetic refrigeration material is characterized in that the chemical general formula of the Cu-doped MnAl-based magnetic refrigeration material is as follows: mnaAlbCucWherein a is 30-40, b is 50, c is 10-20, a + b + c =100, the Curie temperature is 375-402K, the maximum magnetic entropy is 0.89-1.13J/kgK under the condition of 0-1.5T magnetic field, and the coercive force is coercive force<30Oe of a soft magnetic material;
the method comprises the following steps:
(1) preparing metal manganese, metal copper and metal aluminum, wherein the metal manganese is 30-40 parts by mass, the metal aluminum is 50 parts by mass and the metal copper is 10-20 parts by mass;
(2) putting metal manganese, metal copper and metal aluminum into an electric arc melting furnace simultaneously, vacuumizing the electric arc melting furnace, introducing argon to normal pressure, repeating the steps for three times, vacuumizing the electric arc melting furnace, and introducing argon to 0.3-0.8 standard atmospheric pressure, wherein the pressure in the electric arc melting furnace is less than or equal to 6 × 10 during each vacuumizing-3Pa；
(3) Starting an electric arc melting furnace for melting, and cooling to normal temperature along with the furnace after melting to obtain an alloy ingot; when smelting is carried out, the current is 100-200A; in order to ensure the uniformity of the alloy cast ingot, smelting for at least four times, wherein the smelting time is 1-2 min each time, and turning over the material after the previous smelting is finished and then smelting for the next time;
(4) treating the surface of the alloy cast ingot to remove impurities, and then filling the alloy cast ingot into a quartz tube; vacuumizing the quartz tube, sealing, putting the quartz tube into an annealing furnace, and annealing for at least 72 hours at the temperature of 900 +/-10 ℃;
(5) and after the annealing is finished, taking out the quartz tube, performing water quenching to normal temperature, and taking out the metal material from the quartz tube to obtain the Cu-doped MnAl-based magnetic refrigeration material.
2. The method for preparing the Cu-doped MnAl-based magnetic refrigeration material according to claim 1, wherein the purities of the metal manganese, the metal copper and the metal aluminum are all more than or equal to 99.9%.
3. The preparation method of the Cu-doped MnAl-based magnetic refrigeration material as claimed in claim 1, wherein in the step (2), the addition amount of the manganese metal is 3-6% excessive to compensate for the volatilization of the manganese metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811559048.0A CN109616271B (en) | 2018-12-19 | 2018-12-19 | Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811559048.0A CN109616271B (en) | 2018-12-19 | 2018-12-19 | Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109616271A CN109616271A (en) | 2019-04-12 |
| CN109616271B true CN109616271B (en) | 2020-07-31 |
Family
ID=66010656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811559048.0A Active CN109616271B (en) | 2018-12-19 | 2018-12-19 | Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109616271B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009054776A (en) * | 2007-08-27 | 2009-03-12 | Institute Of Physical & Chemical Research | Magnetic refrigeration material, its manufacturing method, and method of altering antiferromagnetic material to ferromagnetic material |
| CN104593625A (en) * | 2015-01-06 | 2015-05-06 | 同济大学 | Preparation method of non-rare earth MnAl permanent magnetic alloy |
| CN106997800A (en) * | 2017-03-10 | 2017-08-01 | 杭州电子科技大学 | One kind is without rare earth MnAlCuC permanent-magnet alloys and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69200340T2 (en) * | 1991-02-05 | 1994-12-22 | Toshiba Kawasaki Kk | Regenerative materials. |
-
2018
- 2018-12-19 CN CN201811559048.0A patent/CN109616271B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009054776A (en) * | 2007-08-27 | 2009-03-12 | Institute Of Physical & Chemical Research | Magnetic refrigeration material, its manufacturing method, and method of altering antiferromagnetic material to ferromagnetic material |
| CN104593625A (en) * | 2015-01-06 | 2015-05-06 | 同济大学 | Preparation method of non-rare earth MnAl permanent magnetic alloy |
| CN106997800A (en) * | 2017-03-10 | 2017-08-01 | 杭州电子科技大学 | One kind is without rare earth MnAlCuC permanent-magnet alloys and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Coercivity enhancement in Mn-Al-Cu flakes produced by surfactant-assisted milling;P. Saravanan等;《APPLIED PHYSICS LETTERS》;20151113;全文 * |
| I Tsuboya.On the New Magnetic Phase in Manganese-Aluminium-copper system.《Journal of the Physical Society of Japan》.1961, * |
| On the New Magnetic Phase in Manganese-Aluminium-copper system;I Tsuboya;《Journal of the Physical Society of Japan》;19611231;第1875-1877页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109616271A (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109108227B (en) | High-flux preparation method of LaFeSi-based magnetic refrigeration material | |
| WO2019169875A1 (en) | High-coercivity neodymium iron boron magnet and preparation method therefor | |
| CN104694813B (en) | LaFeSi base magnetic refrigerating materials and preparation method and application | |
| CN108735411B (en) | Lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and preparation process thereof | |
| WO2021244315A1 (en) | Neodymium-iron-boron magnet material, raw material composition and preparation method and use thereof | |
| WO2021244311A1 (en) | Neodymium-iron-boron magnet material, raw material composition thereof, preparation method therefor, and application thereof | |
| WO2021244312A1 (en) | Neodymium-iron-boron magnet material, raw material composition, and preparation method and application of neodymium-iron-boron magnet material | |
| CN105938757B (en) | A kind of preparation method for improving high abundance rare earth permanent-magnetic material magnetic property | |
| CN111524674A (en) | Neodymium-iron-boron magnet material, raw material composition, preparation method and application | |
| CN109616271B (en) | Cu-doped MnAl-based magnetic refrigeration material and preparation method thereof | |
| Wei et al. | Structural and intrinsic magnetic properties of Sm2Fe17Ny (y= 2–8) | |
| JP7245474B2 (en) | Magnetocaloric alloys useful for magnetic refrigeration applications | |
| CN111524673A (en) | Neodymium-iron-boron magnet material, raw material composition, preparation method and application thereof | |
| CN111540557A (en) | Neodymium-iron-boron magnet material, raw material composition, preparation method and application | |
| WO2021244314A1 (en) | Neodymium-iron-boron magnet material, raw material composition, preparation method therefor and use thereof | |
| CN1025125C (en) | Iron-rare earth-base magnetic refrigerating material and its preparation | |
| CN108277416A (en) | A kind of rare earth high-entropy alloy for magnetic refrigeration | |
| CN110634638B (en) | (Pr, Gd) Co permanent magnet material and preparation method thereof | |
| CN110343934B (en) | Zn-doped Mn-Fe-P-Si-based magnetic refrigeration material and preparation method thereof | |
| CN109801767A (en) | A kind of neodymium cobalt-based magnetic refrigerating material and preparation method thereof with rotation magnetothermal effect | |
| CN115323248B (en) | High-entropy doped lanthanum-iron-silicon-based magnetic refrigeration material with wide refrigeration temperature area and preparation method thereof | |
| CN108486469B (en) | Nanocrystalline La1-xRxFeySizMethod for producing magnetocaloric effect material | |
| CN112927920B (en) | Pressurizing heat treatment method for improving magnetic property of 2:17 type Sm-Co sintered magnet | |
| KR102589531B1 (en) | Magneto-caloric alloy and preparing method thereof | |
| CN109378148B (en) | Lanthanum-iron-silicon-based magnetic refrigeration material and preparation method 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 |