CN105568262B - A kind of preparation method of wear-resistant, damage resistant, corrosion resistant metal surface film layer - Google Patents
A kind of preparation method of wear-resistant, damage resistant, corrosion resistant metal surface film layer Download PDFInfo
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- CN105568262B CN105568262B CN201510998106.XA CN201510998106A CN105568262B CN 105568262 B CN105568262 B CN 105568262B CN 201510998106 A CN201510998106 A CN 201510998106A CN 105568262 B CN105568262 B CN 105568262B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/20—Aqueous dispersion or solution
- B05D2401/21—Mixture of organic solvent and water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2518/00—Other type of polymers
Abstract
The present invention provides a kind of wear-resistant, damage resistant, the preparation method of corrosion resistant metal surface film layer, specially workpiece is handled in the rare-earth salt solution of boiling first, then workpiece is subjected to self-assembled modified processing, workpiece is subjected to chemical bath deposition processing again, workpiece is finally subjected to curing process, produces wear-resistant, damage resistant, corrosion resistant metal surface film layer.Fine micro-nano structure is presented in metal surface film prepared by the present invention, has excellent wear-resistant, damage resistant, corrosion resistance.The inventive method is applied to the surface treatment of the various metals materials such as aluminium, magnesium, copper, titanium, iron, nickel, zinc metal and its alloy.The inventive method have the characteristics that technique be simple and convenient to operate, without specialized instrument and equipment, be easy to heavy industrialization processing.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, and in particular to a kind of wear-resistant, damage resistant, corrosion resistant
The preparation method of metal surface film layer.
Background technology
The metals such as aluminium, magnesium, copper, titanium, iron, nickel, zinc and its alloy are widely used in the every field of national economy.Due to this
A little materials chemistry properties are more active, contact with surrounding medium and easily corrode, and also frequent companion in use
And have a reasons such as abrasion, scuffing and caused by damage.Although current metal surface treating method can slow down to a certain extent
The generation of corrosion, but for by wear, scratch etc. trigger local damage, breakage and then fast erosion and caused by high risks
But very little is acted on.As can be seen here, the film layer that prepared by existing metal surface treating method has that function is more single, can not meet
The defects of complex environment practical application request.Therefore, development is with wear-resistant, damage resistant, corrosion resistant multi-functional metal watch
The related technology of preparing of face mask layer is very necessary and urgent.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide one kind to have wear-resistant, damage resistant, resistance to
The preparation method of the multi-functional metal surface film layer of corrosion.
The object of the present invention is achieved like this：A kind of preparation of wear-resistant, damage resistant, corrosion resistant metal surface film layer
Method, it is characterised in that comprise the following steps：
1. rare-earth salt solution processing of seething with excitement：The metal works of cleaning are immersed in the glass with cover equipped with boiling rare-earth salt solution
In glass container, sealing boiling processing 20 ~ 60 minutes, metal works are then taken out, are dried up with pure water rinsing, compressed air；
The species of the rare-earth salts is the nitrate of lanthanum, samarium, cerium or neodymium；
The concentration of the rare-earth salt solution is 0.0005 ~ 0.0015 mol/L；
The rare-earth salt solution volume and the ratio of metal works area are 100 liters：1 square metre.
2. self-assembled modified processing：Metal works 1. step is handled after soak in 30 ~ 50 DEG C of chitosan solution
10-30 minutes are handled, pure water rinsing is used after taking-up；Again by polymethyl acid solution, pure water, poly- second of the workpiece at 20 ~ 40 DEG C
Soaked respectively in alkene imide liquor, pure water 20 ~ 30 minutes, 3 ~ 5 seconds, 20 ~ 30 minutes, 3 ~ 5 seconds and repeat this alternate immersion
Process 5 ~ 10 times；
The concentration of the chitosan solution is 2 ~ 5 g/l；
The concentration of the polymethyl acid solution is 6 ~ 10 g/l；
The concentration of the polyethylenimine solution is 3 ~ 6 g/l；
The volume of the chitosan solution, polymethyl acid solution and polyethylenimine solution and metal works area
Ratio is 50 liters：1 square metre.
3. chemical bath deposition is handled：Metal works 2. step is handled after respectively 30 ~ 50 DEG C calcium nitrate solution and
Each immersion 10 ~ 30 minutes, use pure water rinsing in sodium carbonate liquor after taking-up；
The concentration of the calcium nitrate solution is 15 ~ 30 g/l；
The concentration of the sodium carbonate liquor is 10 ~ 20 g/l；
The volume of the calcium nitrate solution and sodium carbonate liquor and the ratio of metal works area are 50 liters:1 square metre.
4. curing process：Metal works 3. step is handled after are put into 2 ~ 5 hours of drying in 50 ~ 80 DEG C of baking oven,
Produce wear-resistant, damage resistant, corrosion resistant metal surface film layer.
Further, the metal is the metal and its alloy of aluminium, magnesium, copper, titanium, iron, nickel or zinc.
Compared with prior art, present invention tool has the advantage that：
1st, metal surface film prepared by the present invention is by the rare earth with excellent anti-corrosion capability（Hydrogen）Oxide inner layer film, tool
Self assembly outer membrane by excellent damage resistant ability and the cium carbonate nanoparticles with excellent wear resistance form：Internal layer
Film is to be reacted using the rare-earth salt solution of metal and boiling and be firmly combined with metal surface formation with metal, with essence
The rare earth of trickle micro-nano structure and excellent antiseptic power（Hydrogen）Oxidation film；The self-assembled film of outer layer then using chitosan molecule with it is interior
The hydroxyl strong electrostatic interaction of tunic and combined closely with inner layer film and polymethylacrylic acid, polyethyleneimine in the film layer
Opposite charge, there is very strong electrostatic interaction, Quick cross-linking at scuffing can also be made in corrosive medium, is repaired, thus
Assign film layer excellent damage resistant ability；Chemical bath deposition processing then forms anti abrasive cium carbonate nanoparticles on film surface,
So as to assign film layer excellent wear resistance.
2nd, fine micro-nano structure is presented in the metal surface film for preparing of the present invention, has excellent wear-resistant, damage resistant, resistance to
Corrosive power, overcomes that film layer function prepared by existing metal surface treating method is more single, can not meet complex environment reality
The defects of border application demand.The inventive method preparation process is simple, without specialized instrument and equipment, it is easy to operate, be easy to extensive
Industrial treatment.
3rd, the inventive method is applied widely, can be a variety of in aluminium, magnesium, copper, titanium, iron, nickel, the metal of zinc and its alloy etc.
Metal material surface is prepared with wear-resistant, damage resistant, corrosion resistant multi-functional metal surface film layer.
Brief description of the drawings
Fig. 1 is the microscopic appearance ESEM of skin covering of the surface in embodiment 1（German Zeiss companies, Auriga focused ions
Beam Flied emission scans two-beam Electronic Speculum）Photo, it can be seen that film layer has very fine micro-nano structure.
Fig. 2 is material microphotograph of the skin covering of the surface in different conditions in embodiment 1：(a) initial surface, (b) priority
The surface of wear test and corrosion test is undergone, (c) successively undergoes the surface of Scratch Test and corrosion test.
Embodiment
Metal or alloy is processed into the workpiece that specification is 5cm × 5cm × 0.3cm, it is smooth flat to be polishing to surface with sand paper
It is whole, it is cleaned by ultrasonic in acetone after being rinsed with water 1 ~ 2 minute, obtains the workpiece of surface cleaning.
Embodiment 1：
The preparation method of a kind of wear-resistant, damage resistant, corrosion resistant 2024 aluminum alloy surface film layer, is comprised the following steps that：
1. rare-earth salt solution processing of seething with excitement：2024 Al alloy parts of cleaning are immersed in and rubbed equipped with concentration for 0.0010
You/liter boiling nitric acid cerium mischmetal salting liquid glass container with cover in, sealing boiling processing 30 minutes, then take out workpiece,
Dried up with pure water rinsing, compressed air；
The rare-earth salt solution volume and the ratio of metal works area are 100 liters:1 square metre（Other embodiment is same）.
2. self-assembled modified processing：Workpiece 1. step is handled after is in 40 DEG C of chitosan solutions that concentration is 3 g/l
Immersion treatment 20 minutes, uses pure water rinsing after taking-up；It is again that workpiece is molten for 6 g/l of polymethylacrylic acid in 30 DEG C of concentration
Soaked respectively 30 minutes, 5 seconds, 30 minutes, 5 seconds in liquid, pure water, the polyethylenimine solution that concentration is 3 g/l, pure water
And repeat this 10 times/principle of alternate immersion process；
The volume of the chitosan solution, polymethyl acid solution and polyethylenimine solution and metal works area
Ratio is 50 liters:1 square metre（Other embodiment is same）.
3. chemical bath deposition is handled：The nitric acid that workpiece 2. step is handled after is respectively 20 g/l in 40 DEG C of concentration
Each immersion 20 minutes, use pure water rinsing in the sodium carbonate liquor that calcium solution concentration is 15 g/l after taking-up；
The volume of the calcium nitrate solution and sodium carbonate liquor and the ratio of metal works area are 50 liters:1 square metre
（Other embodiment is same）.
4. curing process：Workpiece 3. step is handled after is put into 4 hours of drying in 60 DEG C of baking oven, produces wear-resisting
Damage, damage resistant, corrosion resistant 2024 aluminum alloy surface film layer.
Metal surface film is wear-resistant, damage resistant, the checking procedure of corrosion-resistant function are as follows（Other embodiment is same）：
A. the specific practice of wear test is：By the tiling of 50# abrasive paper for metallograph on the table, after being handled using the inventive method
Metal works one side contact sand paper（The face is working face）, 100 g counterweight in another face pressure is horizontal, longitudinal direction dragging counterweight is each
100 times, obtain wearing sample.
B. the specific practice of Scratch Test is：Drawn with surface of workpiece of the cutter after using the inventive method processing
Go out about 30 microns of wide cuts together, obtain scratching sample.
C. the specific practice of corrosion test is：Scuffing sample in abrasion sample and b. in a. is soaked in simulation respectively
Seawater corrosion medium is 3.5%（Mass fraction）Take out after 24 hours in sodium chloride solution, dried up with pure water rinsing, cold wind.Corrosion
Medium volume and the ratio of sample area are 50 liters:1 square metre.
D. DM4000M digital-type intelligent material microscopes are utilized（German Leica companies）Abrasion examination is undergone to above-mentioned priority
Test with corrosion test and successively experience Scratch Test and the surface of workpiece film layer of corrosion test observed, and with it is original
The film shape of state is compared, and judges the abrasion, scuffing and corrosion condition of film layer.
Assay：Successively experience wear test and corrosion test and successively experience Scratch Test and the gold of corrosion test
The film layer of metal work-pieces superficial film and reset condition carries out pattern comparison, finds substantially without abrasion, scratches, the vestige of corrosion, card
It is successfully prepared wear-resistant, damage resistant, corrosion resistant metal surface film layer in fact.
Embodiment 2：
The preparation method of a kind of wear-resistant, damage resistant, corrosion resistant AZ61 Mg alloy surfaces film layer, is comprised the following steps that：
1. rare-earth salt solution processing of seething with excitement：The AZ61 magnesium alloy workpieces of cleaning are immersed in and rubbed equipped with concentration for 0.0005
You/liter boiling nitric acid lanthanum rare-earth salt solution glass container with cover in, sealing boiling processing 60 minutes, then take out workpiece,
Dried up with pure water rinsing, compressed air；
2. self-assembled modified processing：Workpiece 1. step is handled after is in 30 DEG C of chitosan solutions that concentration is 2 g/l
Middle immersion treatment 30 minutes, uses pure water rinsing after taking-up；It is again 8 g/l of polymethylacrylic acid in 20 DEG C of concentration by workpiece
Soaked respectively 25 minutes, 4 seconds, 25 minutes, 4 seconds in solution, pure water, the polyethylenimine solution that concentration is 4 g/l, pure water
Clock simultaneously repeats this alternate immersion process 8 times；
3. chemical bath deposition is handled：The nitric acid that workpiece 2. step is handled after is respectively 30 g/l in 30 DEG C of concentration
Each immersion 10 minutes, uses pure water rinsing in calcium solution and the sodium carbonate liquor that concentration is 20 g/l after taking-up；
4. curing process：Workpiece 3. step is handled after is put into 5 hours of drying in 50 DEG C of baking oven, produces wear-resisting
Damage, damage resistant, corrosion resistant AZ61 Mg alloy surfaces film layer.
Assay：Successively experience wear test and corrosion test and successively experience Scratch Test and the gold of corrosion test
The film layer of metal work-pieces superficial film and reset condition carries out pattern comparison, finds substantially without abrasion, scratches, the vestige of corrosion, card
It is successfully prepared wear-resistant, damage resistant, corrosion resistant metal surface film layer in fact.
Embodiment 3：
The preparation method of a kind of wear-resistant, damage resistant, corrosion resistant fine copper superficial film, is comprised the following steps that：
1. rare-earth salt solution processing of seething with excitement：It is 0.0015 mol/L that the fine copper workpiece of cleaning, which is immersed in equipped with concentration,
In the glass container with cover of boiling nitric acid neodymium rare-earth salt solution, sealing boiling processing 20 minutes, workpiece is then taken out, is rushed with pure water
Wash, compressed air drying；
2. self-assembled modified processing：Workpiece 1. step is handled after is in 50 DEG C of chitosan solutions that concentration is 5 g/l
Immersion treatment 10 minutes, uses pure water rinsing after taking-up；It is again that workpiece is molten for 10 g/l of polymethylacrylic acid in 40 DEG C of concentration
Soaked respectively 20 minutes, 3 seconds, 20 minutes, 3 seconds in liquid, pure water, the polyethylenimine solution that concentration is 6 g/l, pure water
And repeat this alternate immersion process 5 times；
3. chemical bath deposition is handled：The nitric acid that workpiece 2. step is handled after is respectively 15 g/l in 50 DEG C of concentration
Each immersion 30 minutes, uses pure water rinsing in calcium solution and the sodium carbonate liquor that concentration is 10 g/l after taking-up；
4. curing process：Workpiece 3. step is handled after is put into 2 hours of drying in 80 DEG C of baking oven, produces wear-resisting
Damage, damage resistant, corrosion resistant fine copper workpiece surface film layer.
Assay：Successively experience wear test and corrosion test and successively experience Scratch Test and the gold of corrosion test
The film layer of metal work-pieces superficial film and reset condition carries out pattern comparison, finds substantially without abrasion, scratches, the vestige of corrosion, card
It is successfully prepared wear-resistant, damage resistant, corrosion resistant metal surface film layer in fact.
Embodiment 4：
The preparation method of a kind of wear-resistant, damage resistant, corrosion resistant pure titanium superficial film, is comprised the following steps that：
1. rare-earth salt solution processing of seething with excitement：It is 0.0010 mol/L that the pure titanium workpiece of cleaning, which is immersed in equipped with concentration,
In the glass container with cover of boiling nitric acid samarium rare-earth salt solution, sealing boiling processing 45 minutes, workpiece is then taken out, is rushed with pure water
Wash, compressed air drying；
2. self-assembled modified processing：Workpiece 1. step is handled after is in 40 DEG C of chitosan solutions that concentration is 4 g/l
Immersion treatment 15 minutes, uses pure water rinsing after taking-up；It is again that workpiece is molten for 7 g/l of polymethylacrylic acid in 30 DEG C of concentration
Soaked respectively 25 minutes, 4 seconds, 25 minutes, 4 seconds in liquid, pure water, the polyethylenimine solution that concentration is 5 g/l, pure water
And repeat this alternate immersion process 6 times；
3. chemical bath deposition is handled：The nitric acid that workpiece 2. step is handled after is respectively 20 g/l in 40 DEG C of concentration
Each immersion 15 minutes, uses pure water rinsing in calcium solution and the sodium carbonate liquor that concentration is 15 g/l after taking-up；
4. curing process：Workpiece 3. step is handled after is put into 3 hours of drying in 70 DEG C of baking oven, produces wear-resisting
Damage, damage resistant, corrosion resistant pure titanium workpiece surface film layer.
Assay：Successively experience wear test and corrosion test and successively experience Scratch Test and the gold of corrosion test
The film layer of metal work-pieces superficial film and reset condition carries out pattern comparison, finds substantially without abrasion, scratches, the vestige of corrosion, card
It is successfully prepared wear-resistant, damage resistant, corrosion resistant metal surface film layer in fact.
Above example is using 2024 aluminium alloys, AZ61 magnesium alloys, fine copper, pure titanium as process object, it is necessary to which explanation is sheet
Invention is equally applicable to other metals and the metal such as alloy and iron, nickel, zinc and its alloy of aluminium, magnesium, copper, titanium.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention, and other are according to the technology of the present invention
The modification or equivalent substitution that scheme is carried out, all should cover among scope of the presently claimed invention.
Claims (2)
1. the preparation method of a kind of wear-resistant, damage resistant, corrosion resistant metal surface film layer, it is characterised in that including following step
Suddenly：
1. rare-earth salt solution processing of seething with excitement：The metal works of cleaning are immersed in into the band cover glass equipped with boiling rare-earth salt solution to hold
In device, sealing boiling processing 20 ~ 60 minutes, metal works are then taken out, are dried up with pure water rinsing, compressed air；
The species of the rare-earth salts is the nitrate of lanthanum, samarium, cerium or neodymium；
The concentration of the rare-earth salt solution is 0.0005 ~ 0.0015 mol/L；
The rare-earth salt solution volume and the ratio of metal works area are 100 liters：1 square metre；
2. self-assembled modified processing：Metal works 1. step is handled after the immersion treatment in 30 ~ 50 DEG C of chitosan solution
10-30 minutes, pure water rinsing is used after taking-up；Again by polymethyl acid solution, pure water, polyethyleneimine of the workpiece at 20 ~ 40 DEG C
Soaked respectively in amine aqueous solution, pure water 20 ~ 30 minutes, 3 ~ 5 seconds, 20 ~ 30 minutes, 3 ~ 5 seconds and repeat this alternate immersion process 5
~ 10 times；
The concentration of the chitosan solution is 2 ~ 5 g/l；
The concentration of the polymethyl acid solution is 6 ~ 10 g/l；
The concentration of the polyethylenimine solution is 3 ~ 6 g/l；
The ratio of the chitosan solution, the volume of polymethyl acid solution and polyethylenimine solution and metal works area
It is 50 liters：1 square metre；
3. chemical bath deposition is handled：Metal works 2. step is handled after are respectively in 30 ~ 50 DEG C of calcium nitrate solution and carbonic acid
Each immersion 10 ~ 30 minutes, use pure water rinsing in sodium solution after taking-up；
The concentration of the calcium nitrate solution is 15 ~ 30 g/l；
The concentration of the sodium carbonate liquor is 10 ~ 20 g/l；
The volume of the calcium nitrate solution and sodium carbonate liquor and the ratio of metal works area are 50 liters:1 square metre；
4. curing process：Metal works 3. step is handled after are put into 2 ~ 5 hours of drying in 50 ~ 80 DEG C of baking oven, produce
Wear-resistant, damage resistant, corrosion resistant metal surface film layer.
2. a kind of wear-resistant, damage resistant according to claim 1, the preparation method of corrosion resistant metal surface film layer, its
It is characterised by, the metal is the metal and its alloy of aluminium, magnesium, copper, titanium, iron, nickel or zinc.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077338A (en) * | 2006-05-24 | 2007-11-28 | 天津大学 | Nano lanthanum carbonate and orally disintegrating tablet and preparation method |
| CN101934268A (en) * | 2010-09-30 | 2011-01-05 | 重庆大学 | Method for preparing magnesium alloy surface super-hydrophobic anticorrosion functional film |
| CN102161773A (en) * | 2011-01-18 | 2011-08-24 | 浙江大学 | Method for preparing organic/inorganic composite honeycomb-patterned ordered film |
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| KR101572545B1 (en) * | 2013-07-25 | 2015-11-27 | 한양대학교 산학협력단 | Oxide electrode materials composite fibers internal mixing electrolyte materials and method for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077338A (en) * | 2006-05-24 | 2007-11-28 | 天津大学 | Nano lanthanum carbonate and orally disintegrating tablet and preparation method |
| CN101934268A (en) * | 2010-09-30 | 2011-01-05 | 重庆大学 | Method for preparing magnesium alloy surface super-hydrophobic anticorrosion functional film |
| CN102161773A (en) * | 2011-01-18 | 2011-08-24 | 浙江大学 | Method for preparing organic/inorganic composite honeycomb-patterned ordered film |
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Effective date of registration: 20200903 Address after: 399 Longfei Road, Meichi Industrial Zone, Yunlong Town, Yinzhou District, Ningbo City, Zhejiang Province Patentee after: NINGBO MORELUX POLE TECHNOLOGY Ltd. Address before: No. 601, No. 5, Longtang West Lane, Longtang community, Minzhi street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Wanzhida Technology Co.,Ltd. Effective date of registration: 20200903 Address after: No. 601, No. 5, Longtang West Lane, Longtang community, Minzhi street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Wanzhida Technology Co.,Ltd. Address before: 400044 Shapingba District Sha Street, No. 174, Chongqing Patentee before: Chongqing University |