CN112080772A - Embedded injection molding connection process for metal and plastic - Google Patents
Embedded injection molding connection process for metal and plastic Download PDFInfo
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- CN112080772A CN112080772A CN202010890405.2A CN202010890405A CN112080772A CN 112080772 A CN112080772 A CN 112080772A CN 202010890405 A CN202010890405 A CN 202010890405A CN 112080772 A CN112080772 A CN 112080772A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 64
- 239000004033 plastic Substances 0.000 title claims abstract description 42
- 229920003023 plastic Polymers 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000001746 injection moulding Methods 0.000 title claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000013043 chemical agent Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 239000004519 grease Substances 0.000 claims abstract description 4
- 239000004576 sand Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000004512 die casting Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 201000004256 Feingold syndrome Diseases 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 206010067171 Regurgitation Diseases 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/02—Light metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses an embedded injection molding connection process of metal and plastic. The technical scheme of the invention is as follows: the method comprises the following steps of ultrasonic degreasing: removing grease on the surface of the metal by using an ultrasonic cleaner; coarsening: the original smooth metal surface is enabled to form a compact sand surface effect through a chemical agent, and the metal combination area is increased; alkali washing: impurities remained in the roughened metal surface are thoroughly removed by alkali washing, and a clean aluminum surface is exposed; neutralizing: removing alkali and metal impurities on the surface of the metal; electrolysis: by electrochemical reaction to obtain a thin layerOxide film Al with numerous compact nano-scale holes2O3(ii) a Micropore processing one and micropore processing two. The scheme provided by the invention can obtain more stable and controllable nano-pores, and the formed nano-pores can enhance the combination of plastics and metals.
Description
Technical Field
The invention relates to the technical field of injection molding connection, in particular to an embedded injection molding connection process of metal and plastic.
Background
With the increasing market demand and the advancement of technology, the device products in most technical fields are becoming thinner and lighter, and the designed structural members must be paid attention to whether the protection and the supporting force are sufficient. The common corresponding technology in the market at present is a metal and plastic nano combination technology, which is generally divided into two steps, firstly, a metal surface is treated by proper chemicals, so that nano-scale fine concave-convex holes are formed on the metal surface; secondly, the processed metal is placed in a mould, plastic is directly injected and molded on the metal surface under the state of heating the metal part, so that the plastic enters the nanometer-scale fine concave-convex holes of the metal part to be firmly adhered to form the metal-plastic integrated molding part, the hole processing procedure is MTN, the procedures comprise ultrasonic degreasing, alkali washing, ultrasonic cleaning, acid washing, ultrasonic cleaning, surface hole forming n1 and surface hole forming n2, the traditional process has the defects that the nanopores formed by chemical reaction exist, phosphoric acid/sulfuric acid has the corrosion capacity on the bonding position of the metal and the plastic, the acid spraying risk exists, and the nanopores formed by the chemical reaction are not stable and controllable enough. The combination of the nano-holes and the plastic is formed, the plastic is easy to enter the nano-holes and cannot be effectively filled, and the combination effect is reduced because the gas trapping phenomenon in the holes is easy to generate due to high pressure maintaining.
Disclosure of Invention
In view of the defects in the prior art, the main object of the present invention is to provide an embedded injection molding connection process that can obtain more stable and controllable nano-holes and can form nano-holes that can enhance the combination of plastic and metal.
In order to achieve the purpose, the invention provides the following technical scheme: an embedded injection molding connection process of metal and plastic comprises the following steps,
s1, ultrasonic degreasing: removing grease on the surface of the metal by using an ultrasonic cleaner;
s2, coarsening: the original smooth metal surface is enabled to form a compact sand surface effect through a chemical agent, and the metal combination area is increased;
s3, alkali washing: impurities remained in the roughened metal surface are thoroughly removed by alkali washing, and a clean aluminum surface is exposed;
s4, neutralization: removing alkali and metal impurities on the surface of the metal;
s5, electrolysis: a layer of thin oxide film Al with numerous compact nano-scale holes is obtained by electrochemical reaction2O3；
S6, first micropore processing: further optimizing the primary micropores generated by the electrochemical reaction by using a chemical agent;
s7, micro-pore processing II: and amine substances are adsorbed in the micropores, and after the plastic is injected into the metal surface, the amine and the resin are subjected to displacement reaction to obtain more effective combination.
Preferably, the electrochemical reaction in the step S5 is 2AL +6OH-> Al2O3+3H2O。
Preferably, the amine substance in step S7 is dimethylamine.
Preferably, the metal is stamped or die cast or extruded aluminum/magnesium and alloys thereof.
Preferably, the plastic is PPS or PBT or PA or TPU or PEEK.
Compared with the prior art, the method has the advantages that the process of the scheme generates primary micropores through electrolysis, and a thin oxide film Al with numerous nano holes can be obtained by utilizing electrochemical reaction2O3. The method has the advantages that the metal surface treatment of the product needs to be performed with anodic oxidation, the key process of pretreatment in the anodic oxidation process comprises a chemical polishing process, and the corrosion capability of phosphoric acid/sulfuric acid in a chemical polishing groove on the metal and plastic combination position can be effectively reduced due to a thin oxidation film of the product produced by the process, so that the probability of acid entering the combination position can be reduced, the acid spitting risk in the anodic oxidation process is reduced, and the MTN has no advantages.
Drawings
FIG. 1 is a surface microstructure of the MMT treated Al6063 of the present invention;
FIG. 2 is a simplified schematic of the combination of metal and plastic with the oxide film after MMT treatment according to the present invention;
FIG. 3 is a combination structure of metal and plastic in a conventional process;
FIG. 4 is a combination structure of metal and plastic according to the present invention;
FIG. 5 is a process of the present invention for the displacement of the amine species in the nanopore;
FIG. 6 is an enlarged sectional view of a combined portion of aluminum metal and plastic according to the present invention;
FIG. 7 is a surface microstructure of metal AZ31B after MMT treatment according to the invention;
FIG. 8 is an enlarged cross-sectional view of the combined parts of AZ31B and plastic;
FIG. 9 is a surface microstructure of metal AZ91D after MMT treatment according to the invention;
fig. 10 is an enlarged sectional view of the joining portion of AZ91D with plastic.
Detailed Description
The invention will be further explained with reference to the drawings.
As shown in fig. 1, an insert injection molding process for connecting metal and plastic comprises the following steps,
s1, ultrasonic degreasing: removing grease on the surface of the metal by using an ultrasonic cleaner;
s2, coarsening: the original smooth metal surface is enabled to form a compact sand surface effect through a chemical agent, and the metal combination area is increased;
s3, alkali washing: impurities remained in the roughened metal surface are thoroughly removed by alkali washing, and a clean aluminum surface is exposed;
s4, neutralization: removing alkali and metal impurities on the surface of the metal;
s5, electrolysis: a layer of thin oxide film Al with numerous compact nano-scale holes is obtained by electrochemical reaction2O3；
S6, first micropore processing: further optimizing the primary micropores generated by the electrochemical reaction by using a chemical agent;
s7, micro-pore processing II: and amine substances are adsorbed in the micropores, and after the plastic is injected into the metal surface, the amine and the resin are subjected to displacement reaction to obtain more effective combination.
Preferably, the electrochemical reaction in the step S5 is 2AL +6OH-> Al2O3+3H2O。
Preferably, the amine substance in step S7 is dimethylamine.
Preferably, the metal is stamped or die cast or extruded aluminum/magnesium and alloys thereof.
Preferably, the plastic is PPS or PBT or PA or TPU or PEEK.
The scheme is that metal (aluminum or magnesium and alloy thereof) is subjected to MMT nano treatment to obtain invisible uniform nano micropores, the invisible uniform nano micropores are directly and effectively combined with plastic, and the nano treatment of the metal part before the metal part is embedded and injection molded is called MMT treatment, hereinafter referred to as MMT process. Compared with the nano-pore formed by the traditional MTN process, the nano-pore can enhance the bonding force of metal and plastic, and the formed nano-pore is more stable and controllable. The traditional MTN process comprises ultrasonic degreasing, alkali washing, ultrasonic cleaning, acid washing, ultrasonic cleaning, surface pore forming n1 and surface pore forming n 2. The nanopore formed by the chemical reaction has the corrosion capacity of phosphoric acid/sulfuric acid on the bonding position of metal and plastic, the acid jetting risk exists, and the nanopore formed by the chemical reaction is not stable and controllable enough. The combination of the nano-holes and the plastic is formed, the plastic is easy to enter the nano-holes and cannot be effectively filled, and the combination effect is reduced because the gas trapping phenomenon in the holes is easy to generate due to high pressure maintaining.
Referring to fig. 2 to 5, the process of the present embodiment generates preliminary micropores by electrolysis, and a thin oxide film Al with numerous nano-pores can be obtained by electrochemical reaction2O3. The method has the advantages that the metal surface treatment of the product needs to be performed with anodic oxidation, the key process of pretreatment in the anodic oxidation process comprises a chemical polishing process, and the corrosion capability of phosphoric acid/sulfuric acid in a chemical polishing groove on the metal and plastic combination position can be effectively reduced due to a thin oxidation film of the product produced by the process, so that the probability of acid entering the combination position can be reduced, the acid spitting risk in the anodic oxidation process is reduced, and the MTN has no advantages.
The bonding force between metal and plastic is stronger, and the metal is aluminum and magnesium to be tested respectively in the following test mode.
The test was performed using standard test pieces with dimensions of 44mm x 18mm x 1.5mm for the metal part, 44mm x 10 x 3mm for the plastic part and 10mm x 5mm for the bonding part, and the tensile tester used was a tensile tester with a tensile speed of 10 mm/min.
As a result of the tensile test, aluminum: in the tensile test, the minimum tensile force is 1826N/0.5cm2Maximum of 1898N/0.5cm2Average 1864N/0.5cm2 (ii) a The surface of the nano-pores has a pore diameter of 20-70 nm, a pore depth of 200-1000nm, and a pore density of 5.3 × 1010 pores/cm2。
Magnesium: in the tensile test, the minimum tensile force of AZ31B is 1480N/0.5cm2Maximum 1780N/0.5cm2Average of 1692N/0.5cm2(ii) a The AZ91D tensile force was 1742N/0.5cm at minimum2，
The maximum is 1853N/0.5cm2Average of 1791N/0.5cm2(ii) a The pore diameter of the nano-pore is 40-140nm, the pore depth is 3-5um, and the pore density is AZ31B: 8/160000nm2 ，AZ91D:24/160000nm2。
Referring to fig. 6 to 10, performance tests compare:
compared with the aspect of nano pores and binding force, the technical treatment effect of the scheme is better than that of an MTN (methanol to toluene) process.
The process treatment and MTN process of the scheme verify the post-anode acid discharge ratio, and the results are shown in the following table:
the anode acid regurgitation is verified by 1000pcs, the MMT proportion is 6.2%, the MTN proportion is 50.1%, a red lead penetration contrast test (MMT VS MTN) is carried out on a certain model at the aluminum-plastic combination gap, the test result shows that 3pcs of the MTN process seriously overflow the red lead, the MMT does not overflow, and the MMT combination is proved to be far better than the MTN.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (5)
1. An embedded injection molding connection process of metal and plastic is characterized in that: comprises the following steps of (a) carrying out,
s1, ultrasonic degreasing: removing grease on the surface of the metal by using an ultrasonic cleaner;
s2, coarsening: the original smooth metal surface is enabled to form a compact sand surface effect through a chemical agent, and the metal combination area is increased;
s3, alkali washing: impurities remained in the roughened metal surface are thoroughly removed by alkali washing, and a clean aluminum surface is exposed;
s4, neutralization: removing alkali and metal impurities on the surface of the metal;
s5, electrolysis: a layer of thin oxide film Al with numerous compact nano-scale holes is obtained by electrochemical reaction2O3；
S6, first micropore processing: further optimizing the primary micropores generated by the electrochemical reaction by using a chemical agent;
s7, micro-pore processing II: and amine substances are adsorbed in the micropores, and after the plastic is injected into the metal surface, the amine and the resin are subjected to displacement reaction to obtain more effective combination.
2. The metal-plastic embedded injection molding connection process according to claim 1, wherein: the electrochemical reaction in the step S5 is 2AL +6OH-> Al2O3+3H2O。
3. The metal-plastic embedded injection molding connection process according to claim 1, wherein: the amine substance in step S7 is dimethylamine.
4. The metal-plastic embedded injection molding connection process according to claim 1, wherein: the metal is aluminum/magnesium and alloy thereof in a stamping or die-casting or extrusion type.
5. The metal-plastic embedded injection molding connection process according to claim 1, wherein: the plastic is PPS or PBT or PA or TPU or PEEK.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010890405.2A CN112080772A (en) | 2020-08-29 | 2020-08-29 | Embedded injection molding connection process for metal and plastic |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010890405.2A CN112080772A (en) | 2020-08-29 | 2020-08-29 | Embedded injection molding connection process for metal and plastic |
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| CN112080772A true CN112080772A (en) | 2020-12-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114717560A (en) * | 2022-03-22 | 2022-07-08 | 深圳市纳明特科技发展有限公司 | Zirconium alloy nano-treatment method |
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|---|---|---|---|---|
| CN103287009A (en) * | 2012-02-24 | 2013-09-11 | 比亚迪股份有限公司 | Preparation method of aluminum alloy-resin composite and aluminum alloy-resin composite prepared by using same |
| CN103341945A (en) * | 2013-06-09 | 2013-10-09 | 东莞劲胜精密组件股份有限公司 | Plastic-metal composite and manufacturing method thereof |
| CN106584761A (en) * | 2016-12-07 | 2017-04-26 | 歌尔股份有限公司 | Nano injection molding method |
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2020
- 2020-08-29 CN CN202010890405.2A patent/CN112080772A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103287009A (en) * | 2012-02-24 | 2013-09-11 | 比亚迪股份有限公司 | Preparation method of aluminum alloy-resin composite and aluminum alloy-resin composite prepared by using same |
| CN103341945A (en) * | 2013-06-09 | 2013-10-09 | 东莞劲胜精密组件股份有限公司 | Plastic-metal composite and manufacturing method thereof |
| CN106584761A (en) * | 2016-12-07 | 2017-04-26 | 歌尔股份有限公司 | Nano injection molding method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114717560A (en) * | 2022-03-22 | 2022-07-08 | 深圳市纳明特科技发展有限公司 | Zirconium alloy nano-treatment method |
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