CN105350049A - Preparing method for graphene oxide composite coating on surface of magnesium alloy - Google Patents
Preparing method for graphene oxide composite coating on surface of magnesium alloy Download PDFInfo
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- CN105350049A CN105350049A CN201510817357.3A CN201510817357A CN105350049A CN 105350049 A CN105350049 A CN 105350049A CN 201510817357 A CN201510817357 A CN 201510817357A CN 105350049 A CN105350049 A CN 105350049A
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- magnesium alloy
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title abstract 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 238000000970 chrono-amperometry Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 229960004418 trolamine Drugs 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 2
- UOFRJXGVFHUJER-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrate Chemical compound [OH-].OCC[NH+](CCO)CCO UOFRJXGVFHUJER-UHFFFAOYSA-N 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000009713 electroplating Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a preparing method for a graphene oxide composite coating on the surface of a magnesium alloy. The preparing method includes the steps that firstly, a magnesium alloy matrix is preprocessed; then, graphene oxide is prepared and dissolved into a 1-5 ml/L triethanolamine water solution and is subjected to ultrasonic dispersing for 2 hours to serve as an electroplating electrolyte; afterwards, a CHI860D type electrochemical workstation is used for assembling a three-electrode system, the preprocessed magnesium alloy serves as a study electrode, a platinum electrode serves as an auxiliary electrode, a saturated calomel electrode serves as a reference electrode, and the chronoamperometry is selected for conducting electrochemical deposition on the magnesium alloy; and finally, the magnesium alloy is taken out to be dried for 1-2 hours at the temperature ranging from 60 DEG C to 70 DEG C, and the graphene oxide composite coating on the surface of the magnesium alloy is obtained. The method is easy to operate, the surface of the obtained composite coating is even and flat, a typical crumple structure of the graphene oxide exists, low corrosion current density and high electrochemical resistance are achieved, and corrosion resistance of the magnesium alloy can be well improved.
Description
Technical field
The invention belongs to metal material surface galvanic corrosion and protection field, particularly a kind of preparation method of Mg alloy surface graphene oxide compound coating.
Background technology
Magnesium alloy, as the very important light metal structure material of one, is described as " 21 century green engineering structural metallic materials ".Magnesium alloy has the irreplaceable property of many other materials, as lightweight, have good castibility and dimensional stability, very strong reproducibility etc., these performances make magnesium alloy be widely used in the fields such as metallurgy, aviation, military affairs, electronics, automotive industry, electrode materials.But the reason of restriction magnesium alloy practical application development most critical is that magnesium alloy has comparatively negative electropotential, is very easily corroded in different complex environments.Graphene oxide has much outstanding physics, chemical property, there is more outstanding aspect ratio and extremely strong barrier property, greatly can extend the path of corrosive medium by matrix, these performances make graphene oxide can improve the corrosion resistance nature of substrate better.Therefore, graphene oxide is a kind of novel material of Corrosion Protection excellence, and application prospect is extensive.But graphene oxide membrane is used for some common metals such as copper, iron and steel and alloy, lessly apply to magnesium alloy.Graphene oxide is applied to magnesium alloy by the present invention innovatively, and in conjunction with the method for galvanic deposit, prepares trolamine/graphene oxide compound coating at Mg alloy surface, improves the corrosion resistance nature of magnesium alloy, widens the practical application area of magnesium alloy.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Mg alloy surface graphene oxide compound coating.
Concrete steps are:
(1) pre-treatment of magnesium alloy
By magnesium alloy successively with the resistance to silicon carbide paper of 600# and 1200# polish step by step, polishing, washing, then oil removing 0.5 ~ 2 minute at 60 ~ 80 DEG C in alkaline degreasing liquid, then through washing, then ultrasonic cleaning 5 ~ 15 minutes in dehydrated alcohol, deionized water ultrasonic cleaning 2 ~ 3 times, cold wind dries up for subsequent use; Described alkaline degreasing liquid formula is: sodium phosphate 20 ~ 30g/L, sodium hydroxide 15 ~ 25g/L, sodium carbonate 30 ~ 40g/L.
(2) preparation of graphene oxide
Graphite oxide is standby by the Hummers legal system improved, the dilute hydrochloric acid solution being 3% by the graphite oxide volume percent of preparation fully washs, it is neutral for being washed till pH value with deionized water again, graphite oxide being put into deionized water for ultrasonic peels off as graphene oxide, be carry out centrifugal treating in the whizzer of 1000 revs/min subsequently at rotating speed by gained graphene oxide suspension, remove the graphite oxide that lower floor does not peel off completely, repeat centrifugal treating more once, obtain supernatant liquid, after lyophilize process, obtain graphene oxide powder.
(3) compound coating preparation
Utilize CHI860D type electrochemical workstation, assembling three-electrode system, be Electrode through step (1) pretreated magnesium alloy, platinum electrode is supporting electrode, saturated calomel electrode is reference electrode, graphene oxide powder 10 ~ the 30mg prepared through step (2) is dissolved in the trolamine aqueous solution of the 1 ~ 5ml/L of 20ml, carries out ultrasonic disperse after 2 hours as electrolytic solution; Select chronoamperometry to carry out electrochemical deposition to magnesium alloy, optimum configurations is: noble potential is-0.90 volt, and low potential is-1.70 volts, step number of times 10 times, pulse width 100 seconds; Magnesium alloy is taken out at 60 ~ 70 DEG C dry 1 ~ 2 hour, i.e. obtained Mg alloy surface graphene oxide compound coating after electrochemical deposition.
Described sodium phosphate, sodium hydroxide, sodium carbonate, dehydrated alcohol, hydrochloric acid, graphite and trolamine are chemical pure and above purity.
Method of the present invention is simple to operate, prepared compound coating surface uniform is smooth, have the typical pleated structure of graphene oxide, and there is lower corrosion electric current density and higher electrochemical impedance, can be good at improving the solidity to corrosion of magnesium alloy, can obtain uniformly for Mg alloy surface process, compound protective coating that solidity to corrosion is high.
Accompanying drawing explanation
Fig. 1 is the SEM figure of Mg alloy surface graphene oxide compound coating prepared by the embodiment of the present invention.
Embodiment
embodiment:
(1) pre-treatment of magnesium alloy
By AZ91 magnesium alloy successively with the resistance to silicon carbide paper of 600# and 1200# polish step by step, polishing, washing, then oil removing 1 minute at 60 DEG C in alkaline degreasing liquid, reusable heat water and cold water is washed samples surface respectively, then ultrasonic cleaning 10 minutes in dehydrated alcohol, deionized water ultrasonic cleaning 3 times, cold wind dries up for subsequent use; Described alkaline degreasing liquid formula is: sodium phosphate 20g/L, sodium hydroxide 20g/L, sodium carbonate 30g/L.
(2) preparation of graphene oxide
Graphite oxide is standby by the Hummers legal system improved, and first with the ice-water bath cooling 120ml vitriol oil, under agitation condition, slowly add 5g Graphite Powder 99, after question response thing mixes completely, system is black in batches; Slowly add 15g potassium permanganate again, now solution is blackish green in batches, reacts 1 hour.React 2 hours in the warm water bath of 40 DEG C afterwards, obtaining product is brown batter shape.Product is moved on to 98 DEG C of water bath with thermostatic control Keep agitation 10 minutes again, and slowly drip 330ml deionized water, product is brown.Drip hydrogen peroxide in product to emerge to bubble-free, coloured product becomes glassy yellow.Filtered while hot, the dilute hydrochloric acid solution being 3% by the graphite oxide volume percent of preparation fully washs, then to be washed till pH value with deionized water be neutral, graphite oxide is put into deionized water for ultrasonic and peels off as graphene oxide.Be carry out centrifugal treating in the whizzer of 1000 revs/min subsequently at rotating speed by gained graphene oxide suspension, remove the graphite oxide that lower floor does not peel off completely, repeat centrifugal treating more once, obtain supernatant liquid, after lyophilize process, obtain graphene oxide powder.
(3) compound coating preparation
Utilize CHI860D type electrochemical workstation, assembling three-electrode system, be Electrode through step (1) pretreated magnesium alloy, platinum electrode is supporting electrode, saturated calomel electrode is reference electrode, the graphene oxide powder 20mg prepared through step (2) is dissolved in the trolamine aqueous solution of the 3ml/L of 20mL, carries out ultrasonic disperse after 2 hours as electrolytic solution.Select chronoamperometry to carry out electrochemical deposition to magnesium alloy, optimum configurations is: noble potential is-0.90 volt, and low potential is-1.70 volts, step number of times 10 times, pulse width 100 seconds.After electrochemical deposition, take out magnesium alloy at 60 DEG C dry 1 hour, obtain Mg alloy surface graphene oxide compound coating.
Described sodium phosphate, sodium hydroxide, sodium carbonate, dehydrated alcohol, sulfuric acid, potassium permanganate, hydrogen peroxide, hydrochloric acid, graphite and trolamine are chemical pure.
The compound coating that the present embodiment obtains is shown by SEM, and whole coating uniform is smooth, has pleated structure, and surface does not have open defect.Shown in spectrogram, to there is the characteristic peak of graphene oxide by XRD.
The compound coating obtained to the present embodiment carries out the test of electrochemistry corrosion resisting property, (magnesium alloy sample with compound coating is Electrode to adopt three-electrode system, platinum electrode is supporting electrode, saturated calomel electrode is reference electrode), corrosive medium to be mass percent concentration be 3.5% NaCl solution.The corrosion electric current density of the compound coating that the present embodiment obtains is 1.104 × 10
-6a/cm
2, than the corrosion electric current density 1.951 × 10 of blank AZ91 magnesium alloy
-5a/cm
2, reduce an order of magnitude, the electrochemical impedance of compound coating reaches 1.010 × 10
4Ω cm
2, than the electrochemical impedance 5.750 × 10 of blank AZ91 magnesium alloy
2Ω cm
2, increase two orders of magnitude, significantly improve the corrosion resisting property of magnesium alloy.
Claims (1)
1. a preparation method for Mg alloy surface graphene oxide compound coating, is characterized in that concrete steps are:
(1) pre-treatment of magnesium alloy
By magnesium alloy successively with the resistance to silicon carbide paper of 600# and 1200# polish step by step, polishing, washing, then oil removing 0.5 ~ 2 minute at 60 ~ 80 DEG C in alkaline degreasing liquid, then through washing, then ultrasonic cleaning 5 ~ 15 minutes in dehydrated alcohol, deionized water ultrasonic cleaning 2 ~ 3 times, cold wind dries up for subsequent use; Described alkaline degreasing liquid formula is: sodium phosphate 20 ~ 30g/L, sodium hydroxide 15 ~ 25g/L, sodium carbonate 30 ~ 40g/L;
(2) preparation of graphene oxide
Graphite oxide is standby by the Hummers legal system improved, the dilute hydrochloric acid solution being 3% by the graphite oxide volume percent of preparation fully washs, it is neutral for being washed till pH value with deionized water again, graphite oxide being put into deionized water for ultrasonic peels off as graphene oxide, be carry out centrifugal treating in the whizzer of 1000 revs/min subsequently at rotating speed by gained graphene oxide suspension, remove the graphite oxide that lower floor does not peel off completely, repeat centrifugal treating more once, obtain supernatant liquid, after lyophilize process, obtain graphene oxide powder;
(3) compound coating preparation
Utilize CHI860D type electrochemical workstation, assembling three-electrode system, be Electrode through step (1) pretreated magnesium alloy, platinum electrode is supporting electrode, saturated calomel electrode is reference electrode, graphene oxide powder 10 ~ the 30mg prepared through step (2) is dissolved in the trolamine aqueous solution of the 1 ~ 5ml/L of 20ml, carries out ultrasonic disperse after 2 hours as electrolytic solution; Select chronoamperometry to carry out electrochemical deposition to magnesium alloy, optimum configurations is: noble potential is-0.90 volt, and low potential is-1.70 volts, step number of times 10 times, pulse width 100 seconds; Magnesium alloy is taken out at 60 ~ 70 DEG C dry 1 ~ 2 hour, i.e. obtained Mg alloy surface graphene oxide compound coating after electrochemical deposition;
Described sodium phosphate, sodium hydroxide, sodium carbonate, dehydrated alcohol, hydrochloric acid, graphite and trolamine are chemical pure and above purity.
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| CN201510817357.3A CN105350049B (en) | 2015-11-23 | 2015-11-23 | A kind of preparation method of Mg alloy surface graphene oxide composite coating |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105648502A (en) * | 2016-03-28 | 2016-06-08 | 桂林理工大学 | Magnesium alloy-surface hydrophobic composite film and preparation method thereof |
| CN106906498A (en) * | 2017-04-06 | 2017-06-30 | 上海电力学院 | A kind of graphene oxide zinc composite plating solution and its preparation method and application |
| CN107354497A (en) * | 2017-06-23 | 2017-11-17 | 河海大学 | A kind of graphenic surface processing improves the corrosion proof method of copper magnesium alloy |
| CN108538643A (en) * | 2018-02-13 | 2018-09-14 | 西安工程大学 | A kind of preparation method of flexibility knitted fabric electrode of super capacitor |
| CN108796571A (en) * | 2018-06-20 | 2018-11-13 | 上海理工大学 | A method of corrosion stability of magnesium alloy is improved using nitrogen-doped graphene quantum dot coating |
| CN109161955A (en) * | 2018-11-07 | 2019-01-08 | 吉林大学 | A kind of electro-deposition preparation method of medical magnesium alloy surface hydroxyapatite and graphene oxide composite biological coating |
| CN109355689A (en) * | 2018-12-11 | 2019-02-19 | 山东工商学院 | The method and its application of super-hydrophobic coat are prepared based on electrodeposition process |
| CN109898122A (en) * | 2019-04-12 | 2019-06-18 | 桂林理工大学 | Magnesium alloy surface micro-arc oxidation/graphene oxide composite film preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105648502A (en) * | 2016-03-28 | 2016-06-08 | 桂林理工大学 | Magnesium alloy-surface hydrophobic composite film and preparation method thereof |
| CN106906498A (en) * | 2017-04-06 | 2017-06-30 | 上海电力学院 | A kind of graphene oxide zinc composite plating solution and its preparation method and application |
| CN107354497A (en) * | 2017-06-23 | 2017-11-17 | 河海大学 | A kind of graphenic surface processing improves the corrosion proof method of copper magnesium alloy |
| CN108538643A (en) * | 2018-02-13 | 2018-09-14 | 西安工程大学 | A kind of preparation method of flexibility knitted fabric electrode of super capacitor |
| CN108796571A (en) * | 2018-06-20 | 2018-11-13 | 上海理工大学 | A method of corrosion stability of magnesium alloy is improved using nitrogen-doped graphene quantum dot coating |
| CN109161955A (en) * | 2018-11-07 | 2019-01-08 | 吉林大学 | A kind of electro-deposition preparation method of medical magnesium alloy surface hydroxyapatite and graphene oxide composite biological coating |
| CN109355689A (en) * | 2018-12-11 | 2019-02-19 | 山东工商学院 | The method and its application of super-hydrophobic coat are prepared based on electrodeposition process |
| CN109898122A (en) * | 2019-04-12 | 2019-06-18 | 桂林理工大学 | Magnesium alloy surface micro-arc oxidation/graphene oxide composite film preparation method |
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| CN105350049B (en) | 2017-12-12 |
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Application publication date: 20160224 Assignee: Guilin Changlong Machinery Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044422 Denomination of invention: A preparation method of graphene oxide composite coating on magnesium alloy surface Granted publication date: 20171212 License type: Common License Record date: 20231026 Application publication date: 20160224 Assignee: Guilin Xinglong Metal Products Processing Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044396 Denomination of invention: A preparation method of graphene oxide composite coating on magnesium alloy surface Granted publication date: 20171212 License type: Common License Record date: 20231027 |