CN104947099A - Preparation method of metal surface film with quick self-repairing capability - Google Patents
Preparation method of metal surface film with quick self-repairing capability Download PDFInfo
- Publication number
- CN104947099A CN104947099A CN201510245080.1A CN201510245080A CN104947099A CN 104947099 A CN104947099 A CN 104947099A CN 201510245080 A CN201510245080 A CN 201510245080A CN 104947099 A CN104947099 A CN 104947099A
- Authority
- CN
- China
- Prior art keywords
- solution
- mol
- concentration
- metal
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a preparation method of a metal surface film with quick self-repairing capability. The preparation method specifically comprises the following steps: performing hydrothermal treatment on a metal in a hydrogen peroxide solution at first, then uniformly coating a polymer sol to the surface of the metal workpiece after the hydrothermal treatment, and drying to solidify the soil, thereby obtaining the metal surface film with the quick self-repairing capability. The metal surface film prepared by the method provided by the invention is very high in self-repairing speed, and a scratch about 80 microns in width can be self-repaired in only 5 seconds. The preparation method provided by the invention is suitable for various metal materials including magnesium, aluminum, zinc, copper, nickel, titanium, zirconium and alloys thereof and steel, and has the characteristics of being simple in process and convenient to operate, needing no special instrument equipment, and being easy to realize large-scale industrialization treatment.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, be specifically related to a kind of metallic surface membrane preparation method with quick self-reparing capability.
Background technology
The metallic substance such as magnesium, aluminium, zinc, copper, steel, iron, nickel, titanium, zirconium are widely used in the every field of national economy.Because these materials chemistry character are more active, for improving its military service quality, extending its work-ing life needs at the certain surface film of its surface preparation usually, as adopted chemical conversion, anodic oxidation, the methods such as differential arc oxidation first form underlying membrane to strengthen the sticking power of rete and metallic matrix, and then on the basis of underlying membrane, form external coating (EC) by application etc. method, although this kind of surface film can provide good protective effect for metallic matrix, but usually not there is self-reparing capability, this just makes metal surface film once due to collision, reasons such as scraping and local damage occurs, breakage just very easily occurs corrode and develop rapidly and cause high risks.So the metal surface film that development has self-reparing capability is significant for the application of metal.But less about the document of metal selfreparing surface film at present, and the self-reparing capability of the rete of report is more weak, realizing repairing needs several hours even time of several days usually.Therefore, be necessary very much to develop as early as possible the metal surface film with quick self-reparing capability to be correlated with technology of preparing.
Summary of the invention
For the problems referred to above that prior art exists, the object of this invention is to provide a kind of metallic surface membrane preparation method with quick self-reparing capability.
The object of the present invention is achieved like this: a kind of metallic surface membrane preparation method with quick self-reparing capability, is characterized in that, comprise the following steps:
1. hydrogen peroxide hydrothermal treatment consists: clean metal works is immersed in and is equipped with in the reactor of hydrogen peroxide solution, reactor sealing is placed in the baking oven of 100 ~ 140 DEG C and is incubated 3 ~ 5 hours, then cool to room temperature, taking-up metal works, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after surface of workpiece, workpiece is dried 28 ~ 36 hours at 40 ~ 60 DEG C, the metal surface film of quick self-reparing capability must be had;
The mass percentage concentration of described hydrogen peroxide solution is 1% ~ 3%.
To be cetyl trimethylammonium bromide, stearyl methacrylate, vinylbenzene, vinylformic acid be described polymeric sol in mass ratio 20 ~ 30,3 ~ 6,0.5 ~ 2,36-50, and Potassium Bromide, potassium pyrosulfite and ammonium persulfate solution are that 100:1 ~ 3:1 ~ 3 are formulated by volume, in described mass ratio mass unit for gram, be 100 milliliters in potassium bromide solution volume; Wherein, the concentration of described potassium bromide solution is 0.1 ~ 0.3 mol/L, and the concentration of pyrosulphite potassium solution is 0.0005 mol/L, and the concentration of ammonium persulfate solution is 0.003 mol/L;
In described coating process, the ratio of polymeric sol volume and metal works treating part area is 50ml ﹕ 1m
2.
Further, the preparation section of described polymeric sol is: added in potassium bromide solution by cetyl trimethylammonium bromide and dissolve, now obtain solution A; Stearyl methacrylate and vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 6 ~ 8 hours, now obtain solution B; In solution B, add vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite and ammonium persulfate solution, ultrasonic mixing successively, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
The concentration of described potassium bromide solution is 0.1 ~ 0.3 mol/L, and volume is 100 milliliters;
Described cetyl trimethylammonium bromide, stearyl methacrylate, vinylbenzene, acrylic acid add-on are respectively 20 ~ 30 grams, 3 ~ 6 grams, 0.5 ~ 2 gram, 36-50 gram;
The concentration of described pyrosulphite potassium solution is 0.0005 mol/L, and volume is 1 ~ 3 milliliter;
The concentration of described ammonium persulfate solution is 0.003 mol/L, and volume is 1 ~ 3 milliliter.
Described metal is magnesium, aluminium, zinc, copper, nickel, titanium, zirconium and alloy thereof or ferrous materials.
Compared to existing technology, the present invention has following advantage:
1, the underlying membrane that the metal surface film that prepared by the present invention is formed by hydrothermal treatment consists and the outer membrane that sol-gel processing is formed form: underlying membrane be utilize react in metal and the hydrogen peroxide high temperature and high pressure environment in reactor and formed in metallic surface one deck and melts combine firmly, have certain microstructure metal (hydrogen) oxide film and gives film surface a large amount of hydroxyls simultaneously, the specific microstructure of this tunic and surperficial a large amount of hydroxyl greatly can strengthen the sticking power of outer membrane and metallic matrix; Outer membrane is made up of the polyacrylic acid supramolecular network structure that cetyltrimethyl ammonium is cation-modified, polyacrylic acid skeleton has very strong electrostatic interaction with between negative charge and the cetyltrimethyl ammonium positively charged ion with positive charge, and rete can be made at scuffing quick crosslinked, self-healing again afterwards.
2, the metal surface film selfreparing speed prepared of the present invention is quickly, and about 80 microns of wide cuts only need 5 seconds just can self-healing, overcome existing selfreparing rete self-reparing capability weak, realize repairing the long defect of required time.The inventive method preparation process is simple, without the need to specialized instrument and equipment, easy to operate, be easy to heavy industrialization process.
3, the inventive method is applied widely, can have the rete of quick self-reparing capability in the preparation of magnesium, aluminium, zinc, copper, nickel, titanium, zirconium and the various metals such as alloy and iron and steel material surface thereof.
Accompanying drawing explanation
Fig. 1 is the microphotograph of surface film self-repair procedure in embodiment 1: from (a) to (g) is followed successively by the microphotograph on 1s, 2s, 3s, 4s, 5s surface after original surface, scratch surface, scuffing.
Embodiment
Metal or alloy is processed into the workpiece that specification is 3cm × 3cm × 0.2cm, smooth to smooth surface with sand papering, ultrasonic cleaning 1 ~ 2 minute in acetone after rinsing with water, obtains the workpiece of surface cleaning.
embodiment 1:
Have an AZ31 Mg alloy surface membrane preparation method for quick self-reparing capability, concrete steps are as follows:
1. hydrogen peroxide hydrothermal treatment consists: being immersed in by clean AZ31 magnesium alloy workpiece and mass percentage concentration is housed is in the reactor of the hydrogen peroxide solution of 1%, reactor sealing is placed in the baking oven of 100 DEG C and is incubated 3 hours, then cool to room temperature, taking-up workpiece, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after workpiece surface, the ratio of sol volume and metal works treating part area is 50ml ﹕ 1m
2, workpiece is dried 28 hours at 60 DEG C, the AZ31 Mg alloy surface film of quick self-reparing capability must be had;
The preparation process of described polymeric sol is: 20 grams of cetyl trimethylammonium bromides being added 100 ml concns is dissolve in 0.1 mol/L potassium bromide solution, now obtains solution A; 3 grams of stearyl methacrylates and 2 grams of vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 6 hours, now obtain solution B; In solution B, add 50 grams of vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite that 1 ml concn is 0.0005 mol/L successively and 1 ml concn is the ammonium persulfate solution of 0.003 mol/L, ultrasonic mixing, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
The checking procedure of metal surface film self-reparing capability is following (other embodiments are same):
Mark about 80 microns of wide cuts together with cutter on film surface, under microscope (German Leica company, DM4000M digital-type intelligent material microscope), observe the repair process of cut, and the time of needs repaired completely in record.
Assay: the quick self-healing of cut, repairs only need 5 seconds kinds completely.
embodiment 2:
Have a fine copper surface film preparation method for quick self-reparing capability, concrete steps are as follows:
1. hydrogen peroxide hydrothermal treatment consists: being immersed in by clean fine copper workpiece and mass percentage concentration is housed is in the reactor of the hydrogen peroxide solution of 3%, reactor sealing is placed in the baking oven of 120 DEG C and is incubated 5 hours, then cool to room temperature, taking-up workpiece, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after workpiece surface, the ratio of sol volume and metal works treating part area is 50ml ﹕ 1m
2, workpiece is dried 36 hours at 40 DEG C, the fine copper surface film of quick self-reparing capability must be had;
The preparation process of described polymeric sol is: 25 grams of cetyl trimethylammonium bromides being added 100 ml concns is dissolve in 0.2 mol/L potassium bromide solution, now obtains solution A; 5 grams of stearyl methacrylates and 1 gram of vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 7 hours, now obtain solution B; In solution B, add 40 grams of vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite that 2 ml concns are 0.0005 mol/L successively and 2 ml concns are the ammonium persulfate solution of 0.003 mol/L, ultrasonic mixing, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
Surface film self-reparing capability assay: the quick self-healing of cut, repairs only need 5 seconds kinds completely.
embodiment 3:
Have 2024 aluminum alloy surface membrane preparation methods of quick self-reparing capability, concrete steps are as follows:
1. hydrogen peroxide hydrothermal treatment consists: being immersed in by 2024 clean Al alloy parts and mass percentage concentration is housed is in the reactor of the hydrogen peroxide solution of 2%, reactor sealing is placed in the baking oven of 110 DEG C and is incubated 4 hours, then cool to room temperature, taking-up workpiece, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after workpiece surface, the ratio of sol volume and metal works treating part area is 50ml ﹕ 1m
2, workpiece is dried 30 hours at 50 DEG C, 2024 aluminum alloy surface films of quick self-reparing capability must be had;
The preparation process of described polymeric sol is: 30 grams of cetyl trimethylammonium bromides being added 100 ml concns is dissolve in 0.3 mol/L potassium bromide solution, now obtains solution A; 6 grams of stearyl methacrylates and 0.5 gram of vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 8 hours, now obtain solution B; In solution B, add 36 grams of vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite that 3 ml concns are 0.0005 mol/L successively and 3 ml concns are the ammonium persulfate solution of 0.003 mol/L, ultrasonic mixing, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
Surface film self-reparing capability assay: the quick self-healing of cut, repairs only need 5 seconds kinds completely.
embodiment 4:
Have an A3 steel surface film preparation method for quick self-reparing capability, concrete steps are as follows:
1. hydrogen peroxide hydrothermal treatment consists: being immersed in by clean A3 steel workpiece and mass percentage concentration is housed is in the reactor of the hydrogen peroxide solution of 2%, reactor sealing is placed in the baking oven of 140 DEG C and is incubated 4 hours, then cool to room temperature, taking-up workpiece, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after workpiece surface, the ratio of sol volume and metal works treating part area is 50ml ﹕ 1m
2, workpiece is dried 32 hours at 50 DEG C, the A3 steel surface film of quick self-reparing capability must be had;
The preparation process of described polymeric sol is: 26 grams of cetyl trimethylammonium bromides being added 100 ml concns is dissolve in 0.25 mol/L potassium bromide solution, now obtains solution A; 4 grams of stearyl methacrylates and 1.5 grams of vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 7 hours, now obtain solution B; In solution B, add 45 grams of vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite that 2 ml concns are 0.0005 mol/L successively and 2 ml concns are the ammonium persulfate solution of 0.003 mol/L, ultrasonic mixing, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
Surface film self-reparing capability assay: the quick self-healing of cut, repairs only need 5 seconds kinds completely.
Above embodiment with AZ31 magnesium alloy, fine copper, 2024 aluminium alloys, A3 steel for handling object, it should be noted that the present invention is equally applicable to magnesium, copper, other metals of aluminium and alloy and zinc, nickel, titanium, the metal of zirconium and alloy, and other ferrous materials.
Finally illustrate, above embodiment is only in order to illustrate technical scheme of the present invention, and the amendment that other foundation technical solution of the present invention are carried out or equivalent replacement, all should be encompassed in the middle of right of the present invention.
Claims (3)
1. there is a metallic surface membrane preparation method for quick self-reparing capability, it is characterized in that, comprise the following steps:
1. hydrogen peroxide hydrothermal treatment consists: clean metal works is immersed in and is equipped with in the reactor of hydrogen peroxide solution, reactor sealing is placed in the baking oven of 100 ~ 140 DEG C and is incubated 3 ~ 5 hours, then cool to room temperature, taking-up metal works, dry up with pure water rinsing, pressurized air;
2. sol coating and solidification: by polymeric sol even application to 1. process after surface of workpiece, workpiece is dried 28 ~ 36 hours at 40 ~ 60 DEG C, the metal surface film of quick self-reparing capability must be had;
The mass percentage concentration of described hydrogen peroxide solution is 1% ~ 3%;
To be cetyl trimethylammonium bromide, stearyl methacrylate, vinylbenzene, vinylformic acid be described polymeric sol in mass ratio 20 ~ 30,3 ~ 6,0.5 ~ 2,36-50, and Potassium Bromide, potassium pyrosulfite and ammonium persulfate solution are that 100:1 ~ 3:1 ~ 3 are formulated by volume, in described mass ratio mass unit for gram, be 100 milliliters in potassium bromide solution volume; Wherein, the concentration of described potassium bromide solution is 0.1 ~ 0.3 mol/L, and the concentration of pyrosulphite potassium solution is 0.0005 mol/L, and the concentration of ammonium persulfate solution is 0.003 mol/L;
In described coating process, the ratio of polymeric sol volume and metal works treating part area is 50ml ﹕ 1m
2.
2. a kind of metallic surface membrane preparation method with quick self-reparing capability according to claim 1, it is characterized in that, the preparation section of described polymeric sol is: added in potassium bromide solution by cetyl trimethylammonium bromide and dissolve, now obtain solution A; Stearyl methacrylate and vinylbenzene are joined in solution A passing under condition of nitrogen gas further, stir 6 ~ 8 hours, now obtain solution B; In solution B, add vinylformic acid, ultrasonic 30 minutes, now obtain solution C; In solution C, add potassium pyrosulfite and ammonium persulfate solution, ultrasonic mixing successively, now obtain solution D; Solution D constant temperature 55 ° is placed 36 hours, obtains colloidal sol;
The concentration of described potassium bromide solution is 0.1 ~ 0.3 mol/L, and volume is 100 milliliters;
Described cetyl trimethylammonium bromide, stearyl methacrylate, vinylbenzene, acrylic acid add-on are respectively 20 ~ 30 grams, 3 ~ 6 grams, 0.5 ~ 2 gram, 36-50 gram;
The concentration of described pyrosulphite potassium solution is 0.0005 mol/L, and volume is 1 ~ 3 milliliter;
The concentration of described ammonium persulfate solution is 0.003 mol/L, and volume is 1 ~ 3 milliliter.
3. a kind of metallic surface membrane preparation method with quick self-reparing capability according to claim 1, it is characterized in that, described metal is magnesium, aluminium, zinc, copper, nickel, titanium, zirconium and alloy thereof or ferrous materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510245080.1A CN104947099B (en) | 2015-05-14 | 2015-05-14 | Preparation method of metal surface film with quick self-repairing capability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510245080.1A CN104947099B (en) | 2015-05-14 | 2015-05-14 | Preparation method of metal surface film with quick self-repairing capability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104947099A true CN104947099A (en) | 2015-09-30 |
| CN104947099B CN104947099B (en) | 2017-04-26 |
Family
ID=54162149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510245080.1A Active CN104947099B (en) | 2015-05-14 | 2015-05-14 | Preparation method of metal surface film with quick self-repairing capability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104947099B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289876A (en) * | 2021-04-30 | 2021-08-24 | 重庆大学 | Preparation method of metal protective film with self-repairing function and super-amphiphobic function |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483661A (en) * | 2003-07-05 | 2004-03-24 | 吉林大学 | Method for preparing tw-dimension ordered nano ring, nano hole and nano self-assembling single layer film |
| US20050234189A1 (en) * | 2004-04-19 | 2005-10-20 | Samsung Electronics Co., Ltd. | Preparation method of latex polymer comprising wax and colorant |
| CN100999563A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of containing emulsion with surfactant low transportting performance |
| CN101659719A (en) * | 2009-09-18 | 2010-03-03 | 中山大学 | Room-temperature self-repairing type thermoplastic polymer material and preparation method thereof |
| CN102850479A (en) * | 2012-08-22 | 2013-01-02 | 华中科技大学 | Preparation method of cationic styrene-acrylic microemulsion |
-
2015
- 2015-05-14 CN CN201510245080.1A patent/CN104947099B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483661A (en) * | 2003-07-05 | 2004-03-24 | 吉林大学 | Method for preparing tw-dimension ordered nano ring, nano hole and nano self-assembling single layer film |
| US20050234189A1 (en) * | 2004-04-19 | 2005-10-20 | Samsung Electronics Co., Ltd. | Preparation method of latex polymer comprising wax and colorant |
| CN100999563A (en) * | 2006-12-29 | 2007-07-18 | 陕西科技大学 | Preparation process of containing emulsion with surfactant low transportting performance |
| CN101659719A (en) * | 2009-09-18 | 2010-03-03 | 中山大学 | Room-temperature self-repairing type thermoplastic polymer material and preparation method thereof |
| CN102850479A (en) * | 2012-08-22 | 2013-01-02 | 华中科技大学 | Preparation method of cationic styrene-acrylic microemulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289876A (en) * | 2021-04-30 | 2021-08-24 | 重庆大学 | Preparation method of metal protective film with self-repairing function and super-amphiphobic function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104947099B (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yin et al. | Influence of specific second phases on corrosion behaviors of Mg-Zn-Gd-Zr alloys | |
| CN102586770B (en) | Method for preparing titanium-zirconium/polyhydroxy esterified product composite conversion coating of aluminum alloy surface | |
| Liu et al. | Study on the mechanism of hydrostatic pressure promoting electrochemical corrosion of pure iron in 3.5% NaCl solution | |
| Kajánek et al. | Corrosion degradation of AZ31 magnesium alloy coated by plasma electrolytic oxidation | |
| Makhlouf | Intelligent stannate-based coatings of self-healing functionality for magnesium alloys | |
| CN104911577A (en) | Chromium-free alkaline passivation solution and passivation method for aluminum alloy | |
| CN109518255A (en) | A kind of compound coatings of Mg alloy surface and preparation method thereof | |
| CN110359048A (en) | A kind of titanium-carbon steel composite board etchant and application method | |
| Li et al. | Effect of chloride ion content on pitting corrosion of dispersion-strengthened-high-strength steel | |
| CN104674322A (en) | Magnesium alloy component differential arc oxidization ceramic membrane, preparation method and electrolyte | |
| Wang et al. | Effect of laser shock peening on corrosion behaviors of ultra-high strength Al-Zn-Mg-Cu alloys prepared by spray forming and ingot metallurgy | |
| Sekar et al. | Enhancement of resistance to galvanic corrosion of ZE41 Mg alloy by equal channel angular pressing | |
| Liu et al. | Corrosion performance of zinc coated steel in seawater environment | |
| CN104947099A (en) | Preparation method of metal surface film with quick self-repairing capability | |
| CN109252200A (en) | A kind of aluminum alloy die casting surface treatment method | |
| Xu et al. | Application of cathodic protection method on steel structures using sacrificial anode and sodium polyacrylate-sodium carboxymethyl cellulose (PANa–CMC) hydrogel electrolyte | |
| Yu et al. | Characterization of Ti-Se conversion coatings on aluminum alloy | |
| CN101974777A (en) | Electrolytic corrosion method of high strength and high toughness Fe-Mn-C series twinning induced plasticity steel | |
| CN114892152A (en) | Method for preparing ionic liquid conversion film on surface of magnesium alloy | |
| Xu et al. | Effects of second phases on the formation mechanism and corrosion resistance of phosphate conversion film on AZ80 Mg alloy | |
| Alam et al. | Surface morphology and corrosion behavior of pure aluminum and its alloys in aqueous sulfuric acid medium | |
| Khoele et al. | Mechanical and Corrosion Behavior of Inconel 718 Nickel-Based Super Alloy Doped with Graphene Nanoplatelets | |
| CN113774374A (en) | Steel-based titanium coating and preparation method and application thereof | |
| Yang et al. | Corrosion behavior of X100 pipeline steel and its heat-affected zones in simulated acidic soil solution | |
| CN114507468A (en) | Magnesium alloy surface photo-thermal self-repairing coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210409 Address after: No. 311, Tuanjie East Road, Qingbaijiang District, Chengdu, Sichuan 610301 Patentee after: CHUANHUA GROUP Co.,Ltd. Address before: 400044 No. 174 Sha Jie street, Shapingba District, Chongqing Patentee before: Chongqing University |
|
| TR01 | Transfer of patent right |