CN106315656B - A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated - Google Patents
A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated Download PDFInfo
- Publication number
- CN106315656B CN106315656B CN201610623761.1A CN201610623761A CN106315656B CN 106315656 B CN106315656 B CN 106315656B CN 201610623761 A CN201610623761 A CN 201610623761A CN 106315656 B CN106315656 B CN 106315656B
- Authority
- CN
- China
- Prior art keywords
- nano
- dysprosium
- dysprosia
- graphene
- nano oxidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on magnesium boride, e.g. MgB2
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Carbon And Carbon Compounds (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of preparation method of the nano oxidized dysprosium of graphene coated, this method comprises the following steps：First, dysprosia nano particle is prepared using pyrolysismethod；2nd, dysprosia nano-pillar is prepared using hydro-thermal method；3rd, graphene oxide solution is prepared；4th, dysprosia nano particle and dysprosia nano-pillar are added in graphene oxide solution, filtered after stirring, obtain filter residue, the filter residue is by being thermally treated resulting in the nano oxidized dysprosium of graphene coated.A kind of in addition, application present invention also offers nano oxidized dysprosium of graphene coated prepared using the above method during binary doped magnesium diboride superconductive bulk is prepared.Present invention process method is simple, using the graphene with high surface area as coating, be advantageous to dysprosia nano particle and dysprosia nano-pillar is evenly dispersed on graphene, reunion is not produced, and is advantageous to improve binary doped magnesium diboride superconductive bulk in low field and High-Field lower critical current density, J c performances.
Description
Technical field
The invention belongs to high temperature superconducting materia technical field, and in particular to a kind of preparation of the nano oxidized dysprosium of graphene coated
Method and its application.
Background technology
Rare earth oxide dysprosia (Dy2O3) there are excellent physicochemical properties, it is widely used in catalysis material, hair
In the fields such as luminescent material, solid fuel cell, pinning magnesium diboride superconductive.When the size of dysprosia particle gradually decreases to nanometer
Size, specific surface area increase produce skin effect, and the surface texture difference of nano oxidized dysprosium causes its reactivity also inconsistent.
In traditional preparation method, nano-oxide is easily reunited, and the more difficult surface for obtaining high activity.
Meanwhile for magnesium diboride super conductive material, in order to improve the performance under magnetic field of mgb 2 superconductor, it is necessary to
By introducing effective pinning center.In conventional methods where, generally use single-element or the doping of hydrocarbon organic matter, such as element
C etc., improve magnesium diboride High-Field lower critical current density, J c performances.But general all its activity of doped source are relatively low, degree of scatter
Difference is, it is necessary to which higher heat treatment temperature could introduce effective doping, and skewness, it is easy to reunites in grain boundaries,
Reduce intercrystalline connectivity.Therefore, nano oxidized dysprosium dispersiveness and activity are improved by graphene coated powder, are introduced into
Into magnesium diboride, realize binary doped, can greatly improve superconductivity.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided a kind of graphene bag
Cover the preparation method of nano oxidized dysprosium.The preparation method is simple, it is easy to accomplish industrialization, using graphene as coating, its
With higher surface area, be advantageous to dysprosia nano particle and dysprosia nano-pillar is evenly dispersed on graphene, do not produce
It is raw to reunite, and the dysprosia nano particle and dysprosia nano-pillar that prepare have different morphologies and the crystal face of high activity, favorably
Binary doped magnesium diboride superconductive bulk is prepared in being subsequently applied to.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of nano oxidized dysprosium of graphene coated
Preparation method, it is characterised in that this method comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 0.1 DEG C/min~10 DEG C/min of heating rate, obtains dysprosia nano particle；The mixing
The volume ratio of ethanol and propionic acid is 1 in solvent:1；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of tert-butylamine or the aqueous solution of amion acetic acid, water is subsequently placed in
In thermal response kettle, dysprosia nano-pillar is obtained after hydro-thermal reaction；Tert-butylamine and water in the aqueous solution of the tert-butylamine
Volume ratio is 1:(4~10)；The volume ratio of the Ammonia In Aqueous Solution guanidine-acetic acid water of the amion acetic acid is 1:(4~10)；
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:(50~100)；Institute
The concentration for stating graphene oxide in graphene oxide solution is 0.5mg/mL~10mg/mL；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:(1~
3) it is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by institute
Filter residue is stated to be placed in heat-treatment furnace, under inert gas shielding, temperature be 400 DEG C~800 DEG C under conditions of be heat-treated 0.5h~
5h, obtain the nano oxidized dysprosium of graphene coated.
The preparation method of the above-mentioned nano oxidized dysprosium of a kind of graphene coated, it is characterised in that heated up described in step 1
Speed is 1 DEG C/min~3 DEG C/min.
The preparation method of the above-mentioned nano oxidized dysprosium of a kind of graphene coated, it is characterised in that moist described in step 1
Oxygen atmosphere in oxygen volumn concentration be 94%~99.4%, surplus is steam.
A kind of preparation method of the above-mentioned nano oxidized dysprosium of graphene coated, it is characterised in that hydro-thermal described in step 2
The temperature of reaction is 120 DEG C~220 DEG C, and the reaction time of the hydro-thermal reaction is 1h~10h.
The preparation method of the above-mentioned nano oxidized dysprosium of a kind of graphene coated, it is characterised in that aoxidized described in step 4
The ratio between the quality of graphene oxide and the gross mass of dysprosia nano particle and dysprosia nano-pillar mixture in graphene solution
For 1:(50~100).
The preparation method of the above-mentioned nano oxidized dysprosium of a kind of graphene coated, it is characterised in that stirred described in step 4
Speed be 100r/min~1000r/min, the time of stirring is 2min~10min.
Meanwhile the nano oxidized dysprosium of graphene coated prepared with the aforedescribed process present invention also offers a kind of profit should
With, it is characterised in that the nano oxidized dysprosium of graphene coated is used to prepare binary doped magnesium diboride superconductive bulk, specific system
It is for process：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:(0.01~
0.2) ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 1h~3h under conditions of being 750 DEG C~850 DEG C, obtains binary doped magnesium diboride superconductive bulk.
Above-mentioned application, it is characterised in that the quality purity of the magnesium powder and boron powder is not less than 99%, the high-purity argon
The quality purity of gas is 99.99%.
Above-mentioned application, it is characterised in that the pressure of the compacting is 10MPa~20MPa.
The present invention has advantages below compared with prior art：
1st, the present invention prepares dysprosia nano particle and dysprosia nano-pillar, and uses graphene coated dysprosia nanometer
Particle and dysprosia nano-pillar, dysprosia nano-pillar can strut the graphene of layer structure, so that dysprosia nano particle quilt
It is coated in the layer structure of graphene, is advantageous to dysprosia nano particle and dysprosia nano-pillar is dispersed in graphene
On, fully inhibit the generation of nano-particle reunion.Meanwhile the crystal face (222) of dysprosia nano-pillar is high activity crystal face, application
Its superconductivity can be improved in preparing binary doped magnesium diboride superconductive bulk.
2nd, the present invention itself has high surface area and reactivity using graphene as coating.Using first wrapping
The processing method cover, restored, be advantageous to dysprosia nanometer and fully combined with graphene and dispersed.Meanwhile graphene sheet
Body, which is alternatively, to be subsequently applied to when preparing binary doped magnesium diboride superconductive bulk as carbon doping source, can more improve magnesium diboride
Superconductivity.
3rd, the present invention can keep the high activity crystal face of nano oxidized dysprosium, be advantageous to the nano oxidized dysprosium of follow-up graphene coated
Applied to binary doped magnesium diboride superconductive bulk is prepared, the reactivity of dysprosium doped thing is improved, phase temperature can be reduced into, more
It is easily accessible the lattice of magnesium diboride.Two kinds of different-shapes and the doping particle dysprosia of size are more beneficial for surpassing in magnesium diboride
Filling in guide block material, improve superconductivity.
4th, preparation method of the present invention is simple, it is easy to accomplish industrialization.
Technical scheme is described in further detail below by drawings and examples.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the nano oxidized dysprosium of graphene coated prepared by the embodiment of the present invention 1.
Embodiment
Embodiment 1
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 2 DEG C/min of heating rate, obtains dysprosia nano particle；The in the mixed solvent ethanol and
The volume ratio of propionic acid is 1:1；The volumn concentration of oxygen is 96.5% in the moist oxygen atmosphere, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of tert-butylamine, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The volume ratio of tert-butylamine and water is 1 in the aqueous solution of the tert-butylamine:7；The hydro-thermal is anti-
The temperature answered is 170 DEG C, and the reaction time of the hydro-thermal reaction is 5.5h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:75；The oxidation
The concentration of graphene oxide is 5mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:2
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 2.5h under conditions of being 600 DEG C, obtains graphene bag
Cover nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nanometer in the graphene oxide solution
The ratio between gross mass of post mixture is 1:100；The speed of the stirring is 550r/min, and the time of stirring is 6min.
Fig. 1 is the scanning electron microscope (SEM) photograph of the nano oxidized dysprosium of graphene coated prepared by the embodiment of the present invention 1, can from figure
Going out a nanometer dysprosia has two kinds of patterns of graininess and column, illustrates to be prepared into by above-mentioned steps one and arrives dysprosia nanometer
Grain, has been prepared dysprosia nano-pillar, and dysprosia nano particle and dysprosia nano-pillar can be equal by above-mentioned steps two
It is scattered in evenly in the layer structure of graphene, is also not present and significantly reunites.It can be seen that dysprosia nano particle
Particle diameter be 10nm~100nm, the length of dysprosia nano-pillar is 300nm~500nm, the diameter 10nm of dysprosia nano-pillar~
30nm, the open and flat ungauged regions of graphene are reunited, and are shown as single-layer graphene.
Meanwhile the nano oxidized dysprosium of graphene coated prepared by embodiment 1 can enter magnesium diboride lattice as doped source,
Improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.1 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 2h under conditions of being 800 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 10MPa.
In 20K, 1T, critical current density jc reaches binary doped magnesium diboride superconductive bulk prepared by the above method
1.2×105A/cm2。
Embodiment 2
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 5 DEG C/min of heating rate, obtains dysprosia nano particle；The in the mixed solvent ethanol and
The volume ratio of propionic acid is 1:1；The volumn concentration of oxygen is 94% in the moist oxygen atmosphere, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of amion acetic acid, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The Ammonia In Aqueous Solution guanidine-acetic acid of the amion acetic acid and the volume ratio of water are 1:4；The hydro-thermal is anti-
The temperature answered is 120 DEG C, and the reaction time of the hydro-thermal reaction is 10h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:50；The oxidation
The concentration of graphene oxide is 0.5mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:1
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 5h under conditions of being 400 DEG C, obtains graphene coated
Nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nano-pillar in the graphene oxide solution
The ratio between gross mass of mixture is 1:85；The speed of the stirring is 100r/min, and the time of stirring is 10min.
Meanwhile the nano oxidized dysprosium of graphene coated manufactured in the present embodiment can enter magnesium diboride lattice as doping
Source, improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.01 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 3h under conditions of being 750 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 15MPa.
For binary doped magnesium diboride superconductive bulk prepared by the above method in 20K, 1T, critical current density jc reaches 1
×105A/cm2。
Embodiment 3
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 1 DEG C/min of heating rate, obtains dysprosia nano particle；The in the mixed solvent ethanol and
The volume ratio of propionic acid is 1:1；The volumn concentration of oxygen is 99.4% in the moist oxygen atmosphere, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of tert-butylamine, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The volume ratio of tert-butylamine and water is 1 in the aqueous solution of the tert-butylamine:10；The hydro-thermal
The temperature of reaction is 220 DEG C, and the reaction time of the hydro-thermal reaction is 1h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:100；The oxidation
The concentration of graphene oxide is 10mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:3
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 0.5h under conditions of being 800 DEG C, obtains graphene bag
Cover nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nanometer in the graphene oxide solution
The ratio between gross mass of post mixture is 1:75；The speed of the stirring is 1000r/min, and the time of stirring is 2min.
Meanwhile the nano oxidized dysprosium of graphene coated manufactured in the present embodiment can enter magnesium diboride lattice as doping
Source, improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.2 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 1h under conditions of being 850 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 20MPa.
For binary doped magnesium diboride superconductive bulk prepared by the above method in 20K, 1T, critical current density jc reaches 7
×104A/cm2。
Embodiment 4
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 0.1 DEG C/min of heating rate, obtains dysprosia nano particle；The in the mixed solvent ethanol
Volume ratio with propionic acid is 1:1；The volumn concentration of oxygen is 94% in the moist oxygen atmosphere, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of amion acetic acid, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The Ammonia In Aqueous Solution guanidine-acetic acid of the amion acetic acid and the volume ratio of water are 1:8；The hydro-thermal is anti-
The temperature answered is 220 DEG C, and the reaction time of the hydro-thermal reaction is 8h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:100；The oxidation
The concentration of graphene oxide is 3mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:2
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 3h under conditions of being 600 DEG C, obtains graphene coated
Nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nano-pillar in the graphene oxide solution
The ratio between gross mass of mixture is 1:85；The speed of the stirring is 800r/min, and the time of stirring is 4min.
Meanwhile the nano oxidized dysprosium of graphene coated manufactured in the present embodiment can enter magnesium diboride lattice as doping
Source, improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.15 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 2h under conditions of being 700 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 15MPa.
For binary doped magnesium diboride superconductive bulk prepared by the above method in 20K, 1T, critical current density jc reaches 1
×105A/cm2。
Embodiment 5
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then in the oxygen atmosphere of humidity
Under, 500 DEG C are continuously heating to by 10 DEG C/min of heating rate, obtains dysprosia nano particle；The in the mixed solvent ethanol
Volume ratio with propionic acid is 1:1；The volumn concentration of oxygen is 96% in the moist oxygen atmosphere, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of tert-butylamine, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The volume ratio of tert-butylamine and water is 1 in the aqueous solution of the tert-butylamine:6；The hydro-thermal is anti-
The temperature answered is 150 DEG C, and the reaction time of the hydro-thermal reaction is 5h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:60；The oxidation
The concentration of graphene oxide is 7mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:3
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 4h under conditions of being 700 DEG C, obtains graphene coated
Nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nano-pillar in the graphene oxide solution
The ratio between gross mass of mixture is 1:50；The speed of the stirring is 300r/min, and the time of stirring is 8min.
Meanwhile the nano oxidized dysprosium of graphene coated manufactured in the present embodiment can enter magnesium diboride lattice as doping
Source, improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.1 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 3h under conditions of being 850 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 20MPa.
For binary doped magnesium diboride superconductive bulk prepared by the above method in 20K, 1T, critical current density jc reaches 9
×104A/cm2。
Embodiment 6
The method that the present embodiment prepares the nano oxidized dysprosium of graphene coated comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium
Solution is placed in pyrolysis reactor furnace, is carried out drying and processing under conditions of being first 120 DEG C in temperature, is then in water vapor partial pressure
Under 2000Pa moist oxygen atmosphere, 500 DEG C are continuously heating to by 7.5 DEG C/min of heating rate, obtains dysprosia nanometer
Particle；The volume ratio of the in the mixed solvent ethanol and propionic acid is 1:1；The volume hundred of oxygen in the moist oxygen atmosphere
It is 98% to divide content, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of amion acetic acid, it is subsequently placed in hydrothermal reaction kettle, through hydro-thermal reaction
After obtain dysprosia nano-pillar；The Ammonia In Aqueous Solution guanidine-acetic acid of the amion acetic acid and the volume ratio of water are 1:7；The hydro-thermal is anti-
The temperature answered is 200 DEG C, and the reaction time of the hydro-thermal reaction is 7h.
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, obtain aoxidizing stone
Black alkene solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:80；The oxidation
The concentration of graphene oxide is 10mg/mL in graphene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:1
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and under inert gas shielding, temperature is heat-treated 2h under conditions of being 800 DEG C, obtains graphene coated
Nano oxidized dysprosium；The quality of graphene oxide and dysprosia nano particle and dysprosia nano-pillar in the graphene oxide solution
The ratio between gross mass of mixture is 1:65；The speed of the stirring is 1000r/min, and the time of stirring is 5min.
Meanwhile the nano oxidized dysprosium of graphene coated manufactured in the present embodiment can enter magnesium diboride lattice as doping
Source, improve superconductivity.
The nano oxidized dysprosium of graphene coated manufactured in the present embodiment is applied to prepare binary doped magnesium diboride superconductive bulk,
Specifically preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:
0.07 ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, protected in high-purity argon gas atmosphere
Under shield, temperature is heat-treated 2h under conditions of being 800 DEG C, obtains binary doped magnesium diboride superconductive bulk；The magnesium powder and boron powder
Quality purity be not less than 99%, the quality purity of the high-purity argon gas is 99.99%；The pressure of the compacting is 15MPa.
For binary doped magnesium diboride superconductive bulk prepared by the above method in 20K, 1T, critical current density jc reaches 8
×104A/cm2。
It is described above, only it is presently preferred embodiments of the present invention, any restrictions is not done to the present invention, it is every according to invention skill
Any simple modification, change and the equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (8)
1. a kind of preparation method of the nano oxidized dysprosium of graphene coated, it is characterised in that this method comprises the following steps：
Step 1: acetic acid dysprosium to be dissolved in the in the mixed solvent of ethanol and propionic acid, acetic acid dysprosium solution is obtained, by the acetic acid dysprosium solution
It is placed in pyrolysis reactor furnace, drying and processing is carried out under conditions of being first 120 DEG C in temperature, then under the oxygen atmosphere of humidity,
500 DEG C are continuously heating to by 0.1 DEG C/min~10 DEG C/min of heating rate, obtains dysprosia nano particle；The ethanol and
The in the mixed solvent ethanol of propionic acid and the volume ratio of propionic acid are 1:1；
The volumn concentration of oxygen is 94%~99.4% in moist oxygen atmosphere described in step 1, and surplus is steam；
Step 2: dysprosium nitrate is dissolved in the aqueous solution of tert-butylamine or the aqueous solution of amion acetic acid, it is anti-to be subsequently placed in hydro-thermal
Answer in kettle, dysprosia nano-pillar is obtained after hydro-thermal reaction；The volume of tert-butylamine and water in the aqueous solution of the tert-butylamine
Than for 1:(4~10)；The Ammonia In Aqueous Solution guanidine-acetic acid of the amion acetic acid and the volume ratio of water are 1:(4~10)；
Step 3: the in the mixed solvent that graphene oxide is added to deionized water and ethanol stirs, graphene oxide is obtained
Solution；The volume ratio of the in the mixed solvent deionized water and ethanol of the deionized water and ethanol is 1:(50~100)；The oxygen
The concentration of graphene oxide is 0.5mg/mL~10mg/mL in graphite alkene solution；
Step 4: dysprosia nano-pillar described in dysprosia nano particle described in step 1 and step 2 is pressed 1:(1~3)
It is added to after mass ratio is well mixed described in step 3 in graphene oxide solution, is filtered after stirring, obtain filter residue, by the filter
Slag is placed in heat-treatment furnace, and in inert gas shielding, temperature is heat-treated 0.5h~5h under conditions of being 400 DEG C~800 DEG C, obtains
The nano oxidized dysprosium of graphene coated.
A kind of 2. preparation method of the nano oxidized dysprosium of graphene coated according to claim 1, it is characterised in that step 1
Described in heating rate be 1 DEG C/min~5 DEG C/min.
A kind of 3. preparation method of the nano oxidized dysprosium of graphene coated according to claim 1, it is characterised in that step 2
Described in hydro-thermal reaction temperature be 120 DEG C~220 DEG C, the reaction time of the hydro-thermal reaction is 1h~10h.
A kind of 4. preparation method of the nano oxidized dysprosium of graphene coated according to claim 1, it is characterised in that step 4
Described in the quality of graphene oxide and dysprosia nano particle and dysprosia nano-pillar mixture in graphene oxide solution
The ratio between gross mass is 1:(50~100).
A kind of 5. preparation method of the nano oxidized dysprosium of graphene coated according to claim 1, it is characterised in that step 4
Described in the speed that stirs be 100r/min~1000r/min, the time of stirring is 2min~10min.
6. a kind of nano oxidized dysprosium of graphene coated prepared such as any one of Claims 1 to 5 claim methods described
Using, it is characterised in that the nano oxidized dysprosium of graphene coated is used to prepare binary doped magnesium diboride superconductive bulk, specifically
Preparation process is：By magnesium powder, boron powder and the nano oxidized dysprosium of graphene coated according to magnesium, boron and dysprosium atomic ratio be 1:2:(0.01
~0.2) ratio mixed grinding, block is then pressed into, then the block is placed in heat-treatment furnace, in high-purity argon gas atmosphere
Protection, temperature are heat-treated 1h~3h under conditions of being 750 DEG C~850 DEG C, obtain binary doped magnesium diboride superconductive bulk.
7. application according to claim 6, it is characterised in that the quality purity of the magnesium powder and boron powder is not less than
99%, the quality purity of the high-purity argon gas is 99.99%.
8. application according to claim 6, it is characterised in that the pressure of the compacting is 10MPa~20MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610623761.1A CN106315656B (en) | 2016-08-02 | 2016-08-02 | A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610623761.1A CN106315656B (en) | 2016-08-02 | 2016-08-02 | A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106315656A CN106315656A (en) | 2017-01-11 |
| CN106315656B true CN106315656B (en) | 2018-01-02 |
Family
ID=57739630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610623761.1A Active CN106315656B (en) | 2016-08-02 | 2016-08-02 | A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106315656B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385375B (en) * | 2017-06-28 | 2020-06-30 | 中国航发北京航空材料研究院 | Preparation method of graphene-modified residual stress sensitive coating |
| DE102017211660B4 (en) * | 2017-07-07 | 2022-10-27 | Albert-Ludwigs-Universität Freiburg | Process for producing a particulate carrier material coated with a graphene-containing material and a sliding element, as well as a sliding element, a mechanical seal and a bearing arrangement |
| CN115007132B (en) * | 2022-06-29 | 2023-05-26 | 南京工业大学 | Carbon nano tube supported dysprosium oxide catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665503A (en) * | 2009-05-08 | 2010-03-10 | 中国科学院上海硅酸盐研究所 | Rare earth coordination compound, rare earth oxide and preparing method thereof |
| CN103066292A (en) * | 2013-01-30 | 2013-04-24 | 同济大学 | Grapheme/rare earth oxide nanometer composite material and preparation method and application thereof |
| CN105502467A (en) * | 2014-09-22 | 2016-04-20 | 常州市卓群纳米新材料有限公司 | Nanometer dysprosium oxide preparation method |
| CN105753486A (en) * | 2016-05-09 | 2016-07-13 | 陈建峰 | Method for preparing compound MgB2 superconductor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150016742A (en) * | 2013-08-05 | 2015-02-13 | 삼성전기주식회사 | Dysprosium oxide nano particle and synthetic method of the same |
-
2016
- 2016-08-02 CN CN201610623761.1A patent/CN106315656B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665503A (en) * | 2009-05-08 | 2010-03-10 | 中国科学院上海硅酸盐研究所 | Rare earth coordination compound, rare earth oxide and preparing method thereof |
| CN103066292A (en) * | 2013-01-30 | 2013-04-24 | 同济大学 | Grapheme/rare earth oxide nanometer composite material and preparation method and application thereof |
| CN105502467A (en) * | 2014-09-22 | 2016-04-20 | 常州市卓群纳米新材料有限公司 | Nanometer dysprosium oxide preparation method |
| CN105753486A (en) * | 2016-05-09 | 2016-07-13 | 陈建峰 | Method for preparing compound MgB2 superconductor |
Non-Patent Citations (4)
| Title |
|---|
| Effect of Rare-Earth Oxides Doping on the Superconductivity and Flux Pinning of MgB2 Superconductor;X.F.Pan等;《J Supercond Nov Magn》;20101203;第24卷;第1611-1616页 * |
| Enhanced higher temperature (20–30K) transport properties and irreversibility field in nano-Dy2O3doped advanced internal Mg infiltration processed MgB2composites;G.Z.Li等;《APPLIED PHYSICS LETTERS》;20140918;第105卷;第112603页 * |
| Hydrothermal Synthesis of Ln(OH)3 Nanorods and the Conversion to Ln2O3(Ln = Eu, Nd, Dy) Nanorods via Annealing Process;Yanhua Zhu等;《Journal of Nanomaterials》;20131231;第1-7页 * |
| Synthesis and characterization of Dy(OH)3and Dy2O3 nanorods and nanosheets;Jun-Gill Kang等;《Ceramics International》;20141124;第41卷;第3999-4006页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106315656A (en) | 2017-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106549163B (en) | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate | |
| CN106898432A (en) | A kind of preparation method of Graphene yttrium niobium copper superconductor | |
| CN108097255B (en) | Porous carbon frame nickel-based catalyst for carbon dioxide reforming reaction and preparation method and use method thereof | |
| CN106315656B (en) | A kind of preparation method and applications of the nano oxidized dysprosium of graphene coated | |
| CN104843708B (en) | A kind of preparation method of tungsten carbide hollow hemisphere | |
| CN105931750A (en) | Method for preparing magnesium diboride superconducting wire with graphene coated boron powder | |
| CN106205861B (en) | Preparation method for graphene-loaded multielement-doped magnesium diboride superconducting bulk material | |
| CN107601564A (en) | A kind of method of alcoholic solvent hot preparation niobic acid tin nanosphere | |
| CN107721429A (en) | Zirconium carbide silicon carbide composite powder body material and preparation method thereof | |
| Fallah-Arani et al. | Enhancement in the performance of BSCCO (Bi-2223) superconductor with functionalized TiO2 nanorod additive | |
| CN105621406A (en) | Nitrogen-doped porous graphite and preparation method thereof | |
| CN110648857A (en) | Preparation method of highly graphitized ultrathin carbon film coated SiC nanowire | |
| Ranot et al. | Solution-processed nanometers thick amorphous carbon-coated boron as an efficient precursor for high-field performance of MgB2 | |
| CN105590756A (en) | Preparation method of micro-nano dimensional graphene/lithium titanate composite negative electrode material | |
| CN110229005B (en) | Novel superconducting material and preparation method thereof | |
| Shadab et al. | Tuning of superconductivity of bulk MgB2 by ball milling and sieving the boron precursor | |
| Cai et al. | Significant enhancement of critical current density in Gly-doped MgB2 bulk by tailoring the formation of MgO | |
| CN107715880B (en) | Preparation method of nanocomposite with non-noble metal particles anchored on graphene sheet, product and application thereof | |
| Li et al. | Research Progress of Electromagnetic Properties of MgB 2 Induced by Carbon-Containing Materials Addition and Process Techniques | |
| CN102351571B (en) | Preparation method of nanosilver-doped yttrium barium copper oxide film | |
| CN106876042A (en) | A kind of method that high-temperature sintering process prepares niobium aluminium superconductor | |
| CN106782897A (en) | A kind of method that high-temperature sintering process prepares yttrium niobium copper superconductor | |
| Yang et al. | Improved superconducting properties in Ti-doped MgB2 prepared by two-step reaction method and high-energy ball milling | |
| Xu et al. | Investigation on MgB2 superconductor doped by nano-Al powder | |
| CN101450804A (en) | Method for preparing metallic nickel nano granule doped MgB2 superconduction material by reduction method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |