CN111362664A - Aluminum-titanium doped silica aerogel/fiber composite material and preparation method thereof - Google Patents
Aluminum-titanium doped silica aerogel/fiber composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111362664A CN111362664A CN202010098050.3A CN202010098050A CN111362664A CN 111362664 A CN111362664 A CN 111362664A CN 202010098050 A CN202010098050 A CN 202010098050A CN 111362664 A CN111362664 A CN 111362664A
- Authority
- CN
- China
- Prior art keywords
- composite material
- aluminum
- fiber composite
- glass fiber
- doped silica
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
Abstract
The invention discloses an aluminum-titanium doped silica aerogel/fiber composite material and a preparation method thereof, wherein absolute ethyl alcohol, hydrochloric acid solution, aluminum chloride hexahydrate and tetrabutyl titanate are added into a reaction kettle, tetraethoxysilane is measured and slowly poured into the reaction kettle, and sol is obtained by stirring; adding a gel accelerator, and continuously stirring to obtain composite sol; dipping a glass fiber felt into the composite sol, and laying the dipped glass fiber felt on a flat plate; placing the glass fiber felt soaked with the composite sol into a plastic box, sealing, carrying out gel aging, and replacing the aged gel/glass fiber composite material by using a solvent; and (3) performing supercritical drying on the gel/glass fiber composite material. According to the invention, the strength and toughness of the aerogel can be enhanced while the heat insulation property of the aerogel is maintained, the high temperature resistance of the silicon dioxide aerogel is improved by doping the aluminum element, and the prepared aerogel/fiber composite material has good stability and heat insulation property.
Description
Technical Field
The invention relates to the field of high-temperature heat insulation materials, in particular to an aluminum-titanium doped silica aerogel/fiber composite material and a preparation method thereof.
Background
With the manufacturing industries such as buildings, electronics, food, chemical engineering and the like and the industries such as national defense and military industry, higher and higher requirements are put forward on heat insulation materials. The silicon dioxide aerogel has high porosity which can reach more than 90 percent, and the porous net-shaped three-dimensional structure effectively reduces the heat transfer of gas phase and solid phase, so the silicon dioxide aerogel has excellent heat insulation performance and has important application prospect in the national key industrial fields of petrochemical industry, building energy conservation, aerospace and the like. It should be observed, however, that pure SiO2The silica aerogel is brittle, has poor mechanical properties, has large change of radiation thermal conductivity when the temperature is increased, and has a low melting point, so that the application of the silica aerogel in the aspects of heat insulation and heat preservation is severely limited, particularly the heat insulation performance at high temperature.
Disclosure of Invention
The invention mainly solves the technical problem of providing an aluminum-titanium doped silica aerogel/fiber composite material and a preparation method thereof, which not only can ensure certain strength and stability, but also can keep lower heat conductivity coefficient at high temperature, and meet the application in the field of high-temperature heat insulation.
In order to solve the technical problems, the invention adopts a technical scheme that: the preparation method of the aluminum-titanium doped silica aerogel/fiber composite material comprises the following steps:
1) preparation of composite sols
Adding a certain amount of absolute ethyl alcohol, a hydrochloric acid solution, aluminum chloride hexahydrate and tetrabutyl titanate into a reaction kettle, stirring until the absolute ethyl alcohol, the hydrochloric acid solution, the aluminum chloride hexahydrate and the tetrabutyl titanate are completely dissolved, measuring ethyl orthosilicate, slowly pouring the ethyl orthosilicate into the reaction kettle to carry out hydrolysis and polycondensation reactions, and controlling the stirring time to be 4.5-5.5 hours to obtain sol; adding a gel accelerator, and continuously stirring for 4-6 min to obtain an aluminum-titanium doped silica composite sol;
2) composite sol impregnated glass fiber mat and gel aging thereof
Soaking the glass fiber felt into the composite sol, taking out after completely and uniformly soaking, and spreading the soaked glass fiber felt on a flat plate; placing the glass fiber felt soaked with the composite sol in a plastic box, sealing, placing in a drying oven at 45-55 ℃ for gel aging, wherein the aging time is 11-13 h, completely soaking the aged gel/glass fiber composite material with a solvent, and replacing once every 11-13 h for 2 times;
3) supercritical drying of gel/glass fiber composite material
And (3) placing the gel/glass fiber composite material subjected to solvent replacement in a supercritical dryer, setting corresponding parameters, and completely drying the gel/glass fiber composite material to finally obtain the aluminum-titanium doped silica aerogel/fiber composite material.
In a preferred embodiment of the invention, the gel accelerator in step 1) is 1-2, propylene oxide.
In a preferred embodiment of the present invention, the doping amount of the aluminum element in the step 1) is 5 wt% to 15 wt% of the silicon element, and the doping amount of the titanium element is 3 wt% to 10 wt% of the silicon element.
In a preferred embodiment of the invention, the concentration of the hydrochloric acid solution in step 1) is 0.01 mol.L-1。
In a preferred embodiment of the invention, the glass fiber mat in step 2) is a high silica glass fiber mat.
In a preferred embodiment of the present invention, the solvent replaced in step 2) is absolute ethanol, isopropanol, n-heptane or n-hexane.
In a preferred embodiment of the invention, the parameter for supercritical drying in step 3) is CO2The flow is 10-12 kg/h, the drying pressure is 20-25 MPa, and the supercritical temperature is 80-100 ℃.
In a preferred embodiment of the present invention, the drying time in step 3) is 12 to 15 hours.
The invention has the beneficial effects that: according to the invention, the aluminum-titanium doped silica aerogel and the glass fiber are compounded, so that the strength and toughness of the aerogel can be enhanced while the heat insulation property of the aerogel is kept, the high temperature resistance of the silica aerogel is improved by doping an aluminum element, the high temperature heat conductivity coefficient of the silica aerogel is reduced by doping a titanium element, and finally the aerogel/fiber composite material has good stability and heat insulation property.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is an SEM photograph of an Al-Ti doped silica aerogel/fiber composite prepared in example 1, on a 100 μm scale, at 400 times magnification;
FIG. 2 is an SEM photograph of the Al-Ti doped silica aerogel/fiber composite prepared in example 1, on a 100 μm scale, at 500 times magnification;
FIG. 3 is an SEM photograph of an Al-Ti doped silica aerogel/fiber composite prepared in example 2, on a 30 μm scale, at a magnification of 1800 times;
FIG. 4 is an SEM photograph of the AlTiAl doped silica aerogel/fiber composite prepared in example 2, on a 100 μm scale, at 500 times magnification;
FIG. 5 is an SEM photograph of the AlTiAl doped silica aerogel/fiber composite prepared in example 3, on a 100 μm scale, at 450 magnification;
FIG. 6 is an SEM photograph of an Al-Ti doped silica aerogel/fiber composite prepared in example 3, on a 100 μm scale, at 500 times magnification;
FIG. 7 is an SEM photograph of the AlTiAl doped silica aerogel/fiber composite prepared in comparative example 1, on a 30 μm scale, at a magnification of 1500;
fig. 8 is an SEM photograph of the aluminum titanium doped silica aerogel/fiber composite prepared in comparative example 1, with a 20 μm scale and a magnification of 2500 times.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: refer to fig. 1 and 2
A preparation method of an aluminum-titanium doped silica aerogel/fiber composite material comprises the following steps:
1) 2000 mL of absolute ethanol and 1000 mL of 0.01 mol/L-1Hydrochloric acid, weighing 100 g of aluminum chloride hexahydrate and 50 g of tetrabutyl titanate, adding the raw material reagents into a reaction kettle together, and stirring until the raw material reagents are completely dissolved; weighing 1000 mL of tetraethoxysilane, adding the tetraethoxysilane into the mixed solution, and controlling the stirring time to be 5 hours to obtain sol; slowly adding 500 mL of 1-2 epoxypropane into the sol, and continuously stirring for 5 min to obtain the aluminum-titanium doped silica composite sol;
2) dipping a cut high silica glass fiber felt of 30 cm × 30 cm × 3 cm into the composite sol, taking out after the dipping is completed, putting the dipped glass fiber felt on a flat plate, paving, putting the dipped glass fiber felt into a plastic box, sealing, putting the glass fiber felt into a 50 ℃ drying oven for gel aging for 12 hours to obtain an aged gel/glass fiber felt sample, adding 1L of absolute ethyl alcohol to perform solvent replacement and sealing on the aged gel/glass fiber composite material, transferring the gel/glass fiber composite material into the 50 ℃ drying oven, replacing once every 12 hours, and replacing twice;
3) placing the gel/glass fiber composite material subjected to solvent replacement in a supercritical dryer, and setting parameters to be CO2The flow rate is 11 kg/h, the drying pressure is 22 MPa, the supercritical temperature is 90 ℃, and the drying time is 13 h, so that the aluminum-titanium doped silica aerogel/fiber composite material is obtained.
The prepared aluminum-titanium doped silicon dioxide aerogel/fiber composite material with the aluminum doping amount of 10 wt% of silicon element and the titanium doping amount of 5 wt% of silicon element has a smooth and wrinkle-free appearance, is better combined with glass fiber, and has a thermal conductivity coefficient of 0.028-0.030W/(m ∙ K) at 25 ℃ and a thermal conductivity coefficient of 0.085-0.088W/(m ∙ K) at high temperature.
Example 2: refer to fig. 3 and 4
A preparation method of an aluminum-titanium doped silica aerogel/fiber composite material comprises the following steps:
the main steps are the same as example 1, except that 50 g of aluminum chloride hexahydrate and 24 g of tetrabutyl titanate are weighed in the step 1), and finally the aluminum-titanium doped silica aerogel/fiber composite material with the aluminum doping amount of 5 wt% of silicon element and the titanium doping amount of 3 wt% of silicon element is obtained.
The prepared aluminum-titanium doped silicon dioxide aerogel/fiber composite material is flat in appearance, free of wrinkles, good in combination of aerogel and glass fibers, and has a heat conductivity coefficient of 0.030-0.035W/(m ∙ K) at 25 ℃ and a heat conductivity coefficient of 0.101-0.110W/(m ∙ K) at high temperature.
Example 3: refer to fig. 5 and 6
The main steps are the same as example 1, except that 150 g of aluminum chloride hexahydrate and 80 g of tetrabutyl titanate are weighed in the step 1), and finally the aluminum-titanium doped silica aerogel/fiber composite material with the aluminum doping amount of 15 wt% of silicon element and the titanium doping amount of 10 wt% of silicon element is obtained.
The prepared aluminum-titanium doped silicon dioxide aerogel/fiber composite material is flat in appearance and free of wrinkles, the aerogel and the glass fiber are well combined, the heat conductivity coefficient is 0.033-0.037W/(m ∙ K) at 25 ℃, and the heat conductivity coefficient is 0.100-0.105W/(m ∙ K) at high temperature.
Comparative example 1: refer to fig. 7 and 8
A preparation method of a silicon dioxide aerogel/glass fiber composite material comprises the steps of removing the step of adding aluminum chloride hexahydrate and tetrabutyl titanate in the steps of the embodiment, and the rest is the same. The prepared sample has a thermal conductivity of 0.037-0.051W/(m ∙ K) at 25 ℃ and a thermal conductivity of 0.190W/(m ∙ K) at high temperature.
In the invention, the optimum formula is that the doping amount of aluminum is 10 wt% of silicon element and the doping amount of titanium is 5 wt% of silicon element, that is, the formula corresponding to embodiment 1, at this time, the aerogel and the glass fiber are well combined, the thermal conductivity of the composite material is 0.028-0.030W/(m ∙ K) at 25 ℃, and the thermal conductivity is 0.085-0.088W/(m ∙ K) at high temperature.
According to the invention, the aluminum-doped silicon dioxide aerogel is compounded with the glass fiber mat to prepare the composite heat-insulating material, so that the good strength and toughness can be kept; after the aluminum element and the titanium element are added, the high-temperature heat-insulating property of the composite material is greatly improved; therefore, the composite material can be suitable for various complex environments, and the application range of the heat insulation material is widened.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (8)
1. The preparation method of the aluminum-titanium doped silica aerogel/fiber composite material is characterized by comprising the following steps of:
1) preparation of composite sols
Adding a certain amount of absolute ethyl alcohol, a hydrochloric acid solution, aluminum chloride hexahydrate and tetrabutyl titanate into a reaction kettle, stirring until the absolute ethyl alcohol, the hydrochloric acid solution, the aluminum chloride hexahydrate and the tetrabutyl titanate are completely dissolved, measuring ethyl orthosilicate, slowly pouring the ethyl orthosilicate into the reaction kettle to carry out hydrolysis and polycondensation reactions, and controlling the stirring time to be 4.5-5.5 hours to obtain sol; adding a gel accelerator, and continuously stirring for 4-6 min to obtain an aluminum-titanium doped silica composite sol;
2) composite sol impregnated glass fiber mat and gel aging thereof
Soaking the glass fiber felt into the composite sol, taking out after completely and uniformly soaking, and spreading the soaked glass fiber felt on a flat plate; placing the glass fiber felt soaked with the composite sol in a plastic box, sealing, placing in a drying oven at 45-55 ℃ for gel aging, wherein the aging time is 11-13 h, completely soaking the aged gel/glass fiber composite material with a solvent, and replacing once every 11-13 h for 2 times;
3) supercritical drying of gel/glass fiber composite material
And (3) placing the gel/glass fiber composite material subjected to solvent replacement in a supercritical dryer, setting corresponding parameters, and completely drying the gel/glass fiber composite material to finally obtain the aluminum-titanium doped silica aerogel/fiber composite material.
2. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof as claimed in claim 1, wherein the gel accelerator in step 1) is 1-2, propylene oxide.
3. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof as claimed in claim 1, wherein the doping amount of aluminum in step 1) is 5 wt% -15 wt% of silicon, and the doping amount of titanium is 3 wt% -10 wt% of silicon.
4. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof as claimed in claim 1, wherein the concentration of the hydrochloric acid solution in step 1) is 0.01 mol.L-1。
5. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof as claimed in claim 1, wherein the glass fiber mat in step 2) is a high silica glass fiber mat.
6. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof according to claim 1, wherein the solvent replaced in step 2) is absolute ethyl alcohol, isopropyl alcohol, n-heptane or n-hexane.
7. The AlTiAl doped silica aerogel/fiber composite and the method for preparing the same according to claim 1, wherein the parameter of supercritical drying in step 3) is CO2The flow is 10-12 kg/h, the drying pressure is 20-25 MPa, and the supercritical temperature is 80-100 ℃.
8. The aluminum-titanium doped silica aerogel/fiber composite material and the preparation method thereof according to claim 1, wherein the drying time in step 3) is 12-15 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010098050.3A CN111362664B (en) | 2020-02-18 | 2020-02-18 | Preparation method of aluminum-titanium doped silicon dioxide aerogel/fiber composite material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010098050.3A CN111362664B (en) | 2020-02-18 | 2020-02-18 | Preparation method of aluminum-titanium doped silicon dioxide aerogel/fiber composite material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111362664A true CN111362664A (en) | 2020-07-03 |
CN111362664B CN111362664B (en) | 2022-04-22 |
Family
ID=71202284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010098050.3A Active CN111362664B (en) | 2020-02-18 | 2020-02-18 | Preparation method of aluminum-titanium doped silicon dioxide aerogel/fiber composite material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111362664B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112047711A (en) * | 2020-07-23 | 2020-12-08 | 北京卫星制造厂有限公司 | Method for improving high-temperature heat-insulating property of nano porous heat-insulating material |
CN112940636A (en) * | 2021-02-03 | 2021-06-11 | 东莞市鸿亿导热材料有限公司 | Aerogel material for electronic products and preparation method thereof |
CN113480287A (en) * | 2021-06-24 | 2021-10-08 | 湖北三江航天红阳机电有限公司 | Preparation method of yttrium-stabilized zirconium dioxide aerogel/fiber composite material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1749214A (en) * | 2005-08-01 | 2006-03-22 | 中国人民解放军国防科学技术大学 | Aerogel heat insulation composite material and its preparing method |
CN102613245A (en) * | 2012-03-22 | 2012-08-01 | 陕西盟创纳米新型材料股份有限公司 | Preparation method of nano-silica aerogels |
KR20130048742A (en) * | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
CN105038496A (en) * | 2015-07-08 | 2015-11-11 | 当涂县科辉商贸有限公司 | Nanometer Al2O3 composite aerosil thermal-insulation heat-preserving paint and preparation method thereof |
CN110627475A (en) * | 2019-10-10 | 2019-12-31 | 湖北三江航天红阳机电有限公司 | Preparation method of aluminum-silicon aerogel heat insulation material |
-
2020
- 2020-02-18 CN CN202010098050.3A patent/CN111362664B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1749214A (en) * | 2005-08-01 | 2006-03-22 | 中国人民解放军国防科学技术大学 | Aerogel heat insulation composite material and its preparing method |
CN102613245A (en) * | 2012-03-22 | 2012-08-01 | 陕西盟创纳米新型材料股份有限公司 | Preparation method of nano-silica aerogels |
KR20130048742A (en) * | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
CN105038496A (en) * | 2015-07-08 | 2015-11-11 | 当涂县科辉商贸有限公司 | Nanometer Al2O3 composite aerosil thermal-insulation heat-preserving paint and preparation method thereof |
CN110627475A (en) * | 2019-10-10 | 2019-12-31 | 湖北三江航天红阳机电有限公司 | Preparation method of aluminum-silicon aerogel heat insulation material |
Non-Patent Citations (1)
Title |
---|
江包家祺 等: "铝掺杂酸性硅溶胶的制备及表征", 《硅酸盐学报》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112047711A (en) * | 2020-07-23 | 2020-12-08 | 北京卫星制造厂有限公司 | Method for improving high-temperature heat-insulating property of nano porous heat-insulating material |
CN112940636A (en) * | 2021-02-03 | 2021-06-11 | 东莞市鸿亿导热材料有限公司 | Aerogel material for electronic products and preparation method thereof |
CN113480287A (en) * | 2021-06-24 | 2021-10-08 | 湖北三江航天红阳机电有限公司 | Preparation method of yttrium-stabilized zirconium dioxide aerogel/fiber composite material |
Also Published As
Publication number | Publication date |
---|---|
CN111362664B (en) | 2022-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111362664B (en) | Preparation method of aluminum-titanium doped silicon dioxide aerogel/fiber composite material | |
CN108929074B (en) | A kind of silicon dioxide aerogel heat-insulating composite material plate and preparation method thereof | |
CN103086692B (en) | Preparation method of blocky SiO2-Y2O3 compound aerogel | |
CN106747628A (en) | A kind of high temperature resistant foam strengthens SiO2Aerogel insulating material and preparation method thereof | |
US9869422B2 (en) | Method for preparing bulk C—AlN composite aerogel with high strength and high temperature resistance | |
CN104402395A (en) | Fiber-reinforced flexible SiO2 aerogel heat-insulation material and preparation method thereof | |
CN104261798A (en) | High-temperature-resistant SiCOB aerogel heat-insulation composite material and preparation method thereof | |
CN103214034A (en) | Preparation method of zirconium oxide-silicon oxide composite aerogel | |
CN109734412B (en) | Secondary drying method for preparing hydrophobic aluminum-silicon aerogel heat insulation material | |
CN114315365B (en) | Silicon carbide aerogel material and preparation method thereof | |
CN103085385A (en) | Polytetrafluoroethylene substrate and preparation method thereof | |
CN106145999B (en) | A kind of bulk La2O3-Al2O3The preparation method of composite aerogel | |
CN111454071A (en) | Rock wool fiber reinforced silica-based high-strength heat insulation composite material and preparation method thereof | |
CN101638237B (en) | Method for quickly preparing silicondioxlde aerogel | |
CN111253144B (en) | Preparation method of titanium-doped silicon dioxide aerogel/fiber composite material | |
CN104311143A (en) | Method for improving oxidization resistance of carbon aerogel composite material | |
CN104355647A (en) | Cr2O3 doped silicon dioxide aerogel material and preparation method thereof | |
CN106186035A (en) | A kind of block La2o3siO2the preparation method of composite aerogel | |
CN109020469A (en) | A kind of SiO2Aeroge/SiC foam composite insulation material and preparation method thereof | |
CN101792327A (en) | Preparation method of alumina oxide matrix porous ceramic material | |
CN108774072B (en) | Rigid heat insulation tile and preparation method thereof | |
CN108439964B (en) | Nano-pore ceramic heat-insulating coiled material and preparation method thereof | |
CN109534351B (en) | Yttrium silicate aerogel nanocomposite and preparation method thereof | |
CN106186034B (en) | A kind of La2O3The preparation method of aerogel particle | |
CN115155470A (en) | Ordered carbon-polysiloxane composite aerogel 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 |