CN117187626B - High-silver light aluminum alloy and processing technology thereof - Google Patents
High-silver light aluminum alloy and processing technology thereof Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 78
- 239000004332 silver Substances 0.000 title claims abstract description 78
- 229910001095 light aluminium alloy Inorganic materials 0.000 title claims abstract description 49
- 238000012545 processing Methods 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims description 53
- 229910045601 alloy Inorganic materials 0.000 claims description 50
- 238000011282 treatment Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 41
- 230000032683 aging Effects 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 238000003723 Smelting Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 229910052582 BN Inorganic materials 0.000 claims description 14
- 238000010622 cold drawing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 230000006866 deterioration Effects 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- 238000004381 surface treatment Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000007712 rapid solidification Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 4
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000967 As alloy Inorganic materials 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002065 alloy metal Inorganic materials 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract description 2
- -1 silver aluminum Chemical compound 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003607 modifier Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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Abstract
The invention relates to the technical field of silver aluminum alloy, in particular to a high-silver light aluminum alloy and a processing technology thereof. In the high-silver light aluminum alloy, the weight ratio of each component is 0.8-1.5% of silver, 0.3-0.7% of iron, 0.1-0.3% of lanthanum, 0.1-0.2% of cerium and the balance of aluminum. In the scheme, silver, iron, lanthanum and cerium are introduced into an aluminum alloy as alloy elements; the total amount of one alloy metal element is low, so that lattice defects are reduced, and the conductivity is enhanced. And secondly, the introduced transition element is iron, and compared with transition metal elements such as vanadium, titanium, cadmium, zirconium and the like, the iron has magnetism, and the rule order of the distribution of iron phases in the aluminum alloy can be increased through the magnetic field arrangement in the casting process, so that the influence of the transition metal elements on the conductivity of the light aluminum alloy is reduced.
Description
Technical Field
The invention relates to the technical field of silver aluminum alloy, in particular to a high-silver light aluminum alloy and a processing technology thereof.
Background
In modern society life, electric power and electricity are indispensable energy sources; and the transmission of electricity is not separated from the wire material. With the continuous development of society, the demand of wire materials is increasing linearly; on the other hand, the traditional lead material is copper lead, but the copper yield in China is lower, most of the copper is dependent on import, and the cost is higher. Therefore, the substitution product for the proper copper wire is urgently found to have important application value.
Pure aluminum and aluminum alloy have the advantages of low density, inherent conductivity, high safety and the like, and are expected to replace copper wires and play a role in power transmission. The existing research shows that: IACS of pure aluminum is 61-64%; but of lower strength; the strength of the aluminum alloy is effectively improved due to the addition of alloy elements, but the conductivity is reduced due to the fact that the strength is increased and crystal defects are involved; therefore, balancing the strength and conductivity of aluminum alloys is an important research direction for aluminum alloy materials. Meanwhile, in the case of aluminum alloy materials, corrosion resistance of aluminum alloy is one of the problems that lead to a reduction in life, and it is necessary to improve corrosion resistance of aluminum alloy materials.
In conclusion, the preparation of the high-silver light aluminum alloy has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a high-silver light aluminum alloy and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the high silver light aluminum alloy comprises, by weight, 0.8-1.5% of silver, 0.3-0.7% of iron, 0.1-0.3% of lanthanum, 0.1-0.2% of cerium and the balance of aluminum.
More optimally, the high-silver light aluminum alloy also comprises 0.1 to 0.15 percent of boron.
More optimally, the processing technology of the high-silver light aluminum alloy comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy in an inert gas atmosphere to obtain Al-6Ce-3B intermediate alloy; performing rapid solidification treatment on the Al-6Ce-3B intermediate alloy to obtain an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 720-760 ℃; heating to 820-860 ℃, adding Al-3B alloy, and continuing smelting; heating to 880-900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800-820 ℃ to obtain mixed aluminum liquid; (2) Preheating an alterant to 500-520 ℃, adding the alterant into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 800-850 ℃; then refining, skimming and degassing are sequentially carried out, and casting is carried out at 700-720 ℃ to obtain a high-silver aluminum alloy ingot;
step 3: carrying out secondary modification, low-temperature aging and air cooling on the high-silver aluminum alloy ingot; cold drawing is carried out for three times continuously; aging at high temperature, and air cooling to obtain the high-silver light aluminum alloy.
More preferably, in the step 2, a magnetic field of 1.2-1.5T is set in the casting process.
More preferably, in step 3, the second modification process is high-pressure torsional deformation treatment, and in the process: the pressure is 2-3 Gpa, and the torsion turns are 8-10 turns; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 650-750 Hz, and the pulse ratio is 1.
More preferably, in step 3, during the low-temperature aging process: the temperature is 150-200 ℃ and the time is 1.5-2.5 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 650-750 Hz, and the pulse ratio is 1; the high-temperature aging process comprises the following steps: the temperature is 400-450 ℃ and the time is 3-4 hours.
More preferably, in step 3, during the process of the continuous three cold drawing treatments: the first drawing rate is 10-12 m/s, and the second drawing rate is 8-10 m/s; the third drawing rate is 5-8 m/s.
More preferably, the specific process of step 3 is: step 3: carrying out secondary modification, low-temperature aging and air cooling on the high-silver aluminum alloy ingot; cold drawing is carried out for three times continuously; spraying boron nitride/Al-10 Ag alloy powder, aging at high temperature, and air cooling to obtain high-silver light aluminum alloy;
the process of spraying boron nitride/Al-10 Ag alloy powder comprises the following steps: nitrogen is adopted as propulsion gas, the working temperature is 300-350 ℃, the working gas pressure is 2MPa, and the powder feeding rate is 30-35 g/min; the spraying thickness is 0.1-0.2 mm; wherein the boron nitride/Al-10 Ag alloy powder is prepared by grinding, compounding and sieving boron nitride and Al-10Ag alloy powder with the mass ratio of (0.1-0.15).
More optimally, the high-silver light aluminum alloy is further subjected to surface treatment, wherein the surface treatment process comprises the following steps: (1) Sequentially dissolving zinc nitrate and ammonium nitrate in water, adding nano boron nitride, uniformly dispersing by ultrasonic, and adjusting pH=7-7.5 to obtain pretreatment liquid; (2) Dissolving sodium molybdate and sodium vanadate in water, and regulating the pH value to be 8.6-8.8 to obtain a modified liquid; (3) Placing the high-silver light aluminum alloy into pretreatment liquid, and pretreating for 5-6 hours at 45-50 ℃; then placing the aluminum alloy into a modifying solution, modifying the aluminum alloy for 2 hours at 45-50 ℃, washing and drying the aluminum alloy to obtain the surface modified high-silver light aluminum alloy.
More optimally, in the pretreatment liquid, the concentration of zinc nitrate is 0.05mol/L, and the concentration of ammonium nitrate is 0.3mol/L; in the modified liquid, the concentration of sodium molybdate is 0.05-0.06 mol/L, and the concentration of sodium vanadate is 0.04-0.05 mol/L.
Compared with the prior art, the beneficial effect that this application reached is:
(1) In the scheme, silver, iron, lanthanum and cerium are introduced into an aluminum alloy as alloy elements; the total amount of one alloy metal element is low, so that lattice defects are reduced, and the conductivity is enhanced. And secondly, the introduced transition element is iron, and compared with transition metal elements such as vanadium, titanium, cadmium, zirconium and the like, the iron has magnetism, and the rule order of the distribution of iron phases in the aluminum alloy can be increased through the magnetic field arrangement in the casting process, so that the influence of the transition metal elements on the conductivity of the light aluminum alloy is reduced.
(2) In the scheme, by introducing high silver content and utilizing the conductivity and thermal stability of silver, the silver is introduced into aluminum to form solid solution, so that the conductivity and thermal stability of the light aluminum alloy are improved. However, the introduction of higher silver content can produce grain precipitation, destroy the crystal structure, promote the crystal growth of grain boundaries, and lead to coarsening of the grains, thereby reducing the mechanical properties of the light aluminum alloy. On the other hand, an increase in the silver content affects the dispersibility of silver in the aluminum alloy, thereby affecting the conductivity.
In the scheme, iron with higher content is introduced, the iron can enhance the strength of the aluminum alloy, and the low content of iron can also have positive influence on the conductivity of the light aluminum alloy; similarly, in the scheme, more iron is introduced than in the prior art, and the defect of coarse grains exists.
Thus, to facilitate doping of high silver, higher iron content; firstly, the doping of silver and iron is induced by introducing two rare earth elements of lanthanum and cerium, so that the formation of coarse crystals is inhibited; wherein, compared with the rare earth element, the two rare earth elements have better synergic introduction performance, the purification capability of cerium is higher than that of lanthanum, more solid atoms are easy to form in aluminum, and lanthanum can effectively refine alpha-Al grains. Secondly, introducing boron element, and forming a modifier by compounding Al-3B alloy and cerium to form a cerium-based modifier, so as to effectively refine grains; and in the smelting process, impurities are effectively purified by reintroduction, and AlB can be formed with aluminum 2 Thereby refining the grains and enhancing the strength of the light aluminum alloy.
(3) In the scheme, firstly, the angle of the iron phase crystal grains is promoted to change under the influence of the magnetic field, so that the ordering and the dispersibility of the arrangement are promoted. Secondly, through high torsion and electric pulse auxiliary treatment in the secondary modification process, the diffusion of silver and iron in the aluminum alloy is effectively promoted, and the uniform distribution of dislocation is promoted; thirdly, low-temperature aging treatment before cold drawing and high-temperature aging treatment after cold drawing are utilized, so that nano silver with consistent arrangement direction and uniform dislocation distribution are formed. By combining multiple processes, the regularity of each item in aluminum is improved, thereby being beneficial to the improvement of conductivity.
(4) To enhance corrosion resistance and heat dissipation, it has been shown that by spraying boron nitride on the alloy surface prior to high temperature aging
Al-10Ag alloy powder and further adhering by using aging temperature; and the layered double hydroxide is formed by pretreatment to form a film, and the molybdenum and vanadium are used for intercalation modification, so that the corrosion resistance performance is effectively improved.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is an electron microscopic view of a lightweight aluminum alloy in example 1;
FIG. 2 is a diagram showing the distribution of aluminum element in electron microscope of the lightweight aluminum alloy in example 1;
FIG. 3 is a diagram showing the silver element distribution of the electron microscope of the lightweight aluminum alloy in example 1;
FIG. 4 is a diagram showing the iron element distribution of the electron microscope of the lightweight aluminum alloy in example 1.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
It should be noted that the manufacturers of all the raw materials according to the present invention include, without any particular limitation: in the following examples, the nano boron nitride product number is BN-500Y, with a purity of 99.9%, provided by yuba (ningbo) new materials limited.
Example 1: a processing technology of a high-silver light aluminum alloy comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy for 6 minutes at 2800K in an argon gas atmosphere to obtain Al-6Ce-3B intermediate alloy; the Al-6Ce-3B intermediate alloy is rapidly solidified in a vacuum rapid quenching furnace, the rotation speed of a copper wheel is 40m/s, and the cooling rate is 10 7 K/S, obtaining an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 750 ℃ for 30 minutes; heating to 850 ℃, adding Al-3B alloy, and continuing smelting for 30 minutes; heating to 900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800 ℃ to obtain mixed aluminum liquid; (2) Preheating modifier to 500 ℃, adding the modifier into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 850 ℃ for 30 minutes; then refining, skimming and degassing are sequentially carried out, and casting is carried out under the magnetic field of 1.5T at 700 ℃ to obtain a high-silver aluminum alloy ingot;
step 3: high-pressure torsion deformation treatment is carried out on the high-silver aluminum alloy ingot, and the process is as follows: the pressure is 3Gpa, and the number of torsion turns is 8; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 700Hz, and the pulse ratio is 1; aging at low temperature, wherein: the temperature is 150 ℃ and the time is 2 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 700Hz, and the pulse ratio is 1; air cooling; and (3) carrying out cold drawing treatment for three times in sequence, wherein: the first drawing rate is 10m/s, and the second drawing rate is 8m/s; the third drawing rate is 6m/s; aging at high temperature, wherein: the temperature is 450 ℃ and the time is 4 hours, and the high-silver light aluminum alloy is obtained through air cooling.
In the scheme, in the Gao Yin aluminum alloy ingot, the components are 1.43% of silver, 0.52% of iron, 0.12% of lanthanum, 0.18% of cerium and 0.12% of boron in weight ratio; the balance being aluminum.
Example 2: a processing technology of a high-silver light aluminum alloy comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy for 6 minutes at 2800K in an argon gas atmosphere to obtain Al-6Ce-3B intermediate alloy; the Al-6Ce-3B intermediate alloy is rapidly solidified in a vacuum rapid quenching furnace, the rotation speed of a copper wheel is 40m/s, and the cooling rate is 10 7 K/S, obtaining an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 750 ℃ for 30 minutes; heating to 850 ℃, adding Al-3B alloy, and continuing smelting for 30 minutes; heating to 900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800 ℃ to obtain mixed aluminum liquid; (2) Preheating modifier to 500 ℃, adding the modifier into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 850 ℃ for 30 minutes; then refining, skimming and degassing are sequentially carried out, and casting is carried out under the magnetic field of 1.2T at 700 ℃ to obtain a high-silver aluminum alloy ingot;
step 3: high-pressure torsion deformation treatment is carried out on the high-silver aluminum alloy ingot, and the process is as follows: the pressure is 2Gpa, and the number of torsion turns is 10; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 750Hz, and the pulse ratio is 1; aging at low temperature, wherein: the temperature is 150 ℃ and the time is 2 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 750Hz, and the pulse ratio is 1; air cooling; and (3) carrying out cold drawing treatment for three times in sequence, wherein: the first drawing rate is 10m/s, and the second drawing rate is 8m/s; the third drawing rate is 6m/s; aging at high temperature, wherein: the temperature is 450 ℃ and the time is 3 hours, and the high-silver light aluminum alloy is obtained through air cooling.
In the scheme, in the Gao Yin aluminum alloy ingot, the components are 0.8% of silver, 0.7% of iron, 0.1% of lanthanum, 0.2% of cerium, 0.15% of boron and the balance of aluminum according to weight ratio.
Example 3: a processing technology of a high-silver light aluminum alloy comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy for 6 minutes at 2800K in an argon gas atmosphere to obtain Al-6Ce-3B intermediate alloy; the Al-6Ce-3B intermediate alloy is rapidly solidified in a vacuum rapid quenching furnace, the rotation speed of a copper wheel is 40m/s, and the cooling rate is 10 7 K/S, obtaining an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 750 ℃ for 30 minutes; heating to 850 ℃, adding Al-3B alloy, and continuing smelting for 30 minutes; heating to 900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800 ℃ to obtain mixed aluminum liquid; (2) Preheating modifier to 500 ℃, adding the modifier into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 850 ℃ for 30 minutes; then refining, skimming and degassing are sequentially carried out, and casting is carried out under the magnetic field of 1.3T at 700 ℃ to obtain a high-silver aluminum alloy ingot;
step 3: high-pressure torsion deformation treatment is carried out on the high-silver aluminum alloy ingot, and the process is as follows: the pressure is 3Gpa, and the number of torsion turns is 8; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 650Hz, and the pulse ratio is 1; aging at low temperature, wherein: the temperature is 200 ℃ and the time is 2 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 650Hz, and the pulse ratio is 1; air cooling; and (3) carrying out cold drawing treatment for three times in sequence, wherein: the first drawing rate is 10m/s, and the second drawing rate is 8m/s; the third drawing rate is 6m/s; aging at high temperature, wherein: and (3) air cooling at 400 ℃ for 4 hours to obtain the high-silver light aluminum alloy.
In the scheme, in the Gao Yin aluminum alloy ingot, the components are 1.5% of silver, 0.3% of iron, 0.3% of lanthanum, 0.1% of cerium, 0.1% of boron and the balance of aluminum according to weight ratio.
Example 4: a processing technology of a high-silver light aluminum alloy comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy for 6 minutes at 2800K in an argon gas atmosphere to obtain Al-6Ce-3B intermediate alloy; the Al-6Ce-3B intermediate alloy is rapidly solidified in a vacuum rapid quenching furnace, the rotation speed of a copper wheel is 40m/s, and the cooling rate is 10 7 K/S, obtaining an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 750 ℃ for 30 minutes; heating to 850 ℃, adding Al-3B alloy, and continuing smelting for 30 minutes; heating to 900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800 ℃ to obtain mixed aluminum liquid; (2) Preheating modifier to 500 ℃, adding the modifier into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 850 ℃ for 30 minutes; then refining, skimming and degassing are sequentially carried out, and casting is carried out under the magnetic field of 1.5T at 700 ℃ to obtain a high-silver aluminum alloy ingot;
step 3: high-pressure torsion deformation treatment is carried out on the high-silver aluminum alloy ingot, and the process is as follows: the pressure is 3Gpa, and the number of torsion turns is 8; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 700Hz, and the pulse ratio is 1; aging at low temperature, wherein: the temperature is 150 ℃ and the time is 2 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 700Hz, and the pulse ratio is 1; air cooling; and (3) carrying out cold drawing treatment for three times in sequence, wherein: the first drawing rate is 10m/s, and the second drawing rate is 8m/s; the third drawing rate is 6m/s; drawing to a final diameter of 1.0mm; spraying boron nitride/Al-10 Ag alloy powder on the surface, wherein in the process: nitrogen is adopted as propulsion gas, the working temperature is 350 ℃, the working gas pressure is 2MPa, and the powder feeding rate is 30g/min; the spraying thickness is 0.1mm; the spraying thickness is 0.1mm; aging at high temperature, wherein: air cooling at 450 ℃ for 4 hours to obtain the high-silver light aluminum alloy;
step 4: (1) Sequentially dissolving zinc nitrate and ammonium nitrate in water, adding nano boron nitride, uniformly dispersing by ultrasonic, and adjusting pH=7-7.5 to obtain pretreatment liquid; (2) Dissolving sodium molybdate and sodium vanadate in water, and regulating the pH value to be 8.8 to obtain a modified liquid; (3) Placing the high-silver light aluminum alloy into a pretreatment liquid, and pretreating for 6 hours at 45 ℃; then placing the aluminum alloy into a modifying solution, modifying the aluminum alloy for 2 hours at 50 ℃, washing and drying the aluminum alloy to obtain the surface modified high-silver light aluminum alloy.
In the scheme, in the Gao Yin aluminum alloy ingot, the components are 1.43% of silver, 0.52% of iron, 0.12% of lanthanum, 0.18% of cerium and 0.12% of boron in weight ratio; the balance being aluminum.
Wherein, in the technical process of spraying boron nitride/Al-10 Ag alloy powder: wherein the boron nitride/Al-10 Ag alloy powder is prepared by grinding, compounding and sieving boron nitride and Al-10Ag alloy powder according to the mass ratio of 10:0.12.
Wherein, the concentration of zinc nitrate is 0.05mol/L, and the concentration of ammonium nitrate is 0.3mol/L; in the modified liquid, the concentration of sodium molybdate is 0.06mol/L, and the concentration of sodium vanadate is 0.04mol/L.
Comparative example 1: referring to example 1, the difference is that: no magnetic field was set during casting, and the rest was the same as in example 1;
comparative example 2: referring to example 1, the difference is that: the high-pressure torsional deformation treatment was not performed, and the rest was the same as in example 1;
comparative example 3: referring to example 1, the difference is that: the procedure of example 1 was followed except that no electric pulse was used for the high-voltage torsional deformation treatment and the low-temperature aging;
comparative example 4: referring to example 1, the difference is that: in the electric pulse assisting process, the frequencies were set to 500Hz, and the rest was the same as in example 1.
Comparative example 5: referring to example 1, the difference is that: the temperature of the high temperature aging was changed to 200℃and the rest was the same as in example 1.
Comparative example 6: referring to example 4, the difference is that: the high silver light aluminum alloy of example 1 was further subjected to the pretreatment and the modification treatment of step 4, and the remainder was the same as in example 4.
Experiment 1: the high silver light aluminum alloys prepared in examples and comparative examples were tested for mechanical properties and electrical conductivity, and tensile test pieces of the size of GB/T228.1-2010A universal material testing machine is adopted to detect the tensile strength under the condition that the tensile rate is 2 mm/min; referring to GB/T12966-2008, digital metal conductivity measuring instrument is adopted to detect +.>And calculating to obtain the standard conductivity of the high-silver light aluminum alloy wire. The data obtained are as follows:
conclusion: the data in the table above indicate that: the high-silver light aluminum alloy prepared by the method has good mechanical property and conductivity. By utilizing casting under a magnetic field, secondary deformation treatment and aging treatment before and after cold drawing, silver and iron are effectively homogenized, ordered dispersibility is enhanced, and conductivity is improved on the basis of enhancing mechanical properties. In fig. 1 to 4, the dispersibility of silver and iron in the high silver light aluminum alloy is also fully represented.
Comparing the data of comparative examples 1 to 5 with example 1, it can be found that: the arrangement of the magnetic field can improve the conductivity; the high-pressure torsional deformation treatment can enhance the mechanical property and improve the conductivity; the electric pulse auxiliary treatment can assist in enhancing the performance of the aluminum alloy, meanwhile, the frequency in the electric pulse auxiliary treatment needs to be limited, and the performance is reduced at a lower frequency; furthermore, the final high temperature ageing temperature should be defined, at lower temperatures the ageing conductivity decreases.
Experiment 2: the high-silver light aluminum alloy and the surface modified high-silver light aluminum alloy prepared in example 1, example 4 and comparative example 6 were subjected to electrochemical impedance test at room temperature with 3.5wt% sodium chloride as a solution for judging corrosion resistance.
Conclusion: the corrosion current of example 1 was 0.35×10 -6 A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Whereas in example 4 the corrosion current was 0.29X 10 - 7 A/cm 2 The corrosion current in comparative example 6 was 0.62X10 -7 A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Effectively shows that the boron nitride treatment and the surface modification treatment can effectively enhance the corrosion resistance.
Finally, it should be noted that: the foregoing is merely a preferred example of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A processing technology of a high-silver light aluminum alloy is characterized in that: the method comprises the following steps:
step 1: smelting high-purity cerium and Al-3B alloy in an inert gas atmosphere to obtain Al-6Ce-3B intermediate alloy; performing rapid solidification treatment on the Al-6Ce-3B intermediate alloy to obtain an alterant;
step 2: (1) Smelting high-purity aluminum, al-10Ag alloy and Al-10Fe alloy at 720-760 ℃; heating to 820-860 ℃, adding Al-3B alloy, and continuing smelting; heating to 880-900 ℃, adding Al-10La alloy, smelting and mixing, and preserving heat to 800-820 ℃ to obtain mixed aluminum liquid; (2) Preheating an alterant to 500-520 ℃, adding the alterant into the mixed aluminum liquid, and carrying out ultrasonic homogenization; performing first deterioration treatment at 800-850 ℃; then refining, skimming and degassing are sequentially carried out, and casting is carried out on the alloy ingot at 700-720 ℃ and setting a magnetic field of 1.2-1.5T, so as to obtain a high-silver aluminum alloy ingot;
step 3: carrying out second modification on the high-silver aluminum alloy ingot, wherein the second modification process is high-pressure torsion deformation treatment, and the process comprises the following steps: the pressure is 2-3 Gpa, and the torsion turns are 8-10 turns; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 18A, the frequency is 650-750 Hz, and the pulse ratio is 1; aging at low temperature, wherein: the temperature is 150-200 ℃ and the time is 1.5-2.5 hours; in the process, electric pulse auxiliary treatment is used, the pulse voltage is 30V, the pulse current is 15A, the frequency is 650-750 Hz, the pulse ratio is 1, and the air cooling is carried out; cold drawing is carried out for three times continuously; aging at high temperature, wherein: air cooling at 400-450 deg.c for 3-4 hr to obtain light aluminum alloy with high silver content;
in the high-silver light aluminum alloy, the weight ratio of each component is 0.8-1.5% of silver, 0.3-0.7% of iron, 0.1-0.3% of lanthanum, 0.1-0.2% of cerium, 0.1-0.15% of boron and the balance of aluminum.
2. The process for processing the high-silver light aluminum alloy according to claim 1, wherein the process comprises the following steps of: in the step 3, in the process of the continuous three times of cold drawing treatment: the first drawing rate is 10-12 m/s, and the second drawing rate is 8-10 m/s; the third drawing rate is 5-8 m/s.
3. The process for processing the high-silver light aluminum alloy according to claim 1, wherein the process comprises the following steps of: the specific process of the step 3 is as follows: step 3: carrying out secondary modification, low-temperature aging and air cooling on the high-silver aluminum alloy ingot; cold drawing is carried out for three times continuously; spraying boron nitride/Al-10 Ag alloy powder, aging at high temperature, and air cooling to obtain high-silver light aluminum alloy;
the process of spraying boron nitride/Al-10 Ag alloy powder comprises the following steps: nitrogen is adopted as propulsion gas, the working temperature is 300-350 ℃, the working gas pressure is 2MPa, and the powder feeding rate is 30-35 g/min; the spraying thickness is 0.1-0.2 mm; wherein the boron nitride/Al-10 Ag alloy powder is prepared by grinding, compounding and sieving boron nitride and Al-10Ag alloy powder with the mass ratio of (0.1-0.15).
4. A process for manufacturing a high silver light aluminum alloy according to claim 3, wherein: the high silver light aluminum alloy is further subjected to surface treatment, wherein the surface treatment process comprises the following steps: (1) Sequentially dissolving zinc nitrate and ammonium nitrate in water, adding nano boron nitride, uniformly dispersing by ultrasonic, and adjusting pH=7-7.5 to obtain pretreatment liquid; (2) Dissolving sodium molybdate and sodium vanadate in water, and regulating the pH value to be 8.6-8.8 to obtain a modified liquid; (3) Placing the high-silver light aluminum alloy into pretreatment liquid, and pretreating for 5-6 hours at 45-50 ℃; then placing the aluminum alloy into a modifying solution, modifying the aluminum alloy for 2 hours at 45-50 ℃, washing and drying the aluminum alloy to obtain the surface modified high-silver light aluminum alloy.
5. The process for processing the high-silver light aluminum alloy according to claim 4, wherein the process comprises the following steps of: in the pretreatment liquid, the concentration of zinc nitrate is 0.05mol/L, and the concentration of ammonium nitrate is 0.3mol/L; in the modified liquid, the concentration of sodium molybdate is 0.05-0.06 mol/L, and the concentration of sodium vanadate is 0.04-0.05 mol/L.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616696A (en) * | 2004-12-03 | 2005-05-18 | 云南冶金集团总公司 | High conductivity aluminium base material containing rare-earth and boron and preparing method |
| CN101974709A (en) * | 2010-09-21 | 2011-02-16 | 安徽欣意电缆有限公司 | Super-soft aluminum alloy conductor and preparation method thereof |
| CN104294120A (en) * | 2014-09-15 | 2015-01-21 | 安徽欣意电缆有限公司 | Al-Fe-Cu-Ag aluminum alloy for coal mine cable as well as aluminum alloy cable and preparation method of aluminum alloy cable |
| CN105441730A (en) * | 2015-12-03 | 2016-03-30 | 黄波 | Silver-neodymium-boron containing aluminum alloy conductor and preparation method thereof |
| CN106504813A (en) * | 2016-11-15 | 2017-03-15 | 四川欣意迈科技有限公司 | A kind of rare earth aluminium alloy communication power cable and preparation method thereof |
| CN106521249A (en) * | 2016-12-22 | 2017-03-22 | 四川欣意迈科技有限公司 | Rare silver aluminum alloy conductive wire and preparation method thereof |
| CN106834824A (en) * | 2017-02-17 | 2017-06-13 | 昆明冶金研究院 | It is a kind of containing scandium, the high strength and high conductivity rate alumina-base material of yttrium and preparation method thereof |
| CN111440969A (en) * | 2020-04-09 | 2020-07-24 | 洛阳丰铜伟业金属材料科技发展有限公司 | Preparation process of high-purity aluminum strip for transformer |
| CN113737061A (en) * | 2021-08-26 | 2021-12-03 | 贵州晟展峰新材料科技有限公司 | Nano rare earth aluminum alloy material, preparation method and nano rare earth aluminum alloy rod |
-
2023
- 2023-08-03 CN CN202310972434.7A patent/CN117187626B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616696A (en) * | 2004-12-03 | 2005-05-18 | 云南冶金集团总公司 | High conductivity aluminium base material containing rare-earth and boron and preparing method |
| CN101974709A (en) * | 2010-09-21 | 2011-02-16 | 安徽欣意电缆有限公司 | Super-soft aluminum alloy conductor and preparation method thereof |
| CN104294120A (en) * | 2014-09-15 | 2015-01-21 | 安徽欣意电缆有限公司 | Al-Fe-Cu-Ag aluminum alloy for coal mine cable as well as aluminum alloy cable and preparation method of aluminum alloy cable |
| CN105441730A (en) * | 2015-12-03 | 2016-03-30 | 黄波 | Silver-neodymium-boron containing aluminum alloy conductor and preparation method thereof |
| CN106504813A (en) * | 2016-11-15 | 2017-03-15 | 四川欣意迈科技有限公司 | A kind of rare earth aluminium alloy communication power cable and preparation method thereof |
| CN106521249A (en) * | 2016-12-22 | 2017-03-22 | 四川欣意迈科技有限公司 | Rare silver aluminum alloy conductive wire and preparation method thereof |
| CN106834824A (en) * | 2017-02-17 | 2017-06-13 | 昆明冶金研究院 | It is a kind of containing scandium, the high strength and high conductivity rate alumina-base material of yttrium and preparation method thereof |
| CN111440969A (en) * | 2020-04-09 | 2020-07-24 | 洛阳丰铜伟业金属材料科技发展有限公司 | Preparation process of high-purity aluminum strip for transformer |
| CN113737061A (en) * | 2021-08-26 | 2021-12-03 | 贵州晟展峰新材料科技有限公司 | Nano rare earth aluminum alloy material, preparation method and nano rare earth aluminum alloy rod |
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