CN118099892B - Corrosion-resistant copper terminal and processing technology thereof - Google Patents
Corrosion-resistant copper terminal and processing technology thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 136
- 239000010949 copper Substances 0.000 title claims abstract description 136
- 238000005260 corrosion Methods 0.000 title claims abstract description 44
- 230000007797 corrosion Effects 0.000 title claims abstract description 44
- 238000012545 processing Methods 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 71
- 238000007747 plating Methods 0.000 claims abstract description 63
- 239000002096 quantum dot Substances 0.000 claims abstract description 45
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000003607 modifier Substances 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 19
- -1 quaternary ammonium salt compound Chemical class 0.000 claims description 18
- 238000003754 machining Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- CNLKZIJTTIRBGK-UHFFFAOYSA-N 1-sulfanylimidazolidine-2,4-dione Chemical compound SN1CC(=O)NC1=O CNLKZIJTTIRBGK-UHFFFAOYSA-N 0.000 claims description 12
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims description 10
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 235000017281 sodium acetate Nutrition 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- LWEGEAWFSZTHML-UHFFFAOYSA-L disodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;copper Chemical compound [Na+].[Na+].[Cu].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O LWEGEAWFSZTHML-UHFFFAOYSA-L 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- CAACQKBQSPQWGE-UHFFFAOYSA-N [Co].[Na].[Na].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O Chemical compound [Co].[Na].[Na].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O CAACQKBQSPQWGE-UHFFFAOYSA-N 0.000 claims description 8
- AZMMUMQYPBKXHS-UHFFFAOYSA-N gold sodium Chemical compound [Na].[Au] AZMMUMQYPBKXHS-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 5
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 5
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 claims description 5
- 229960004308 acetylcysteine Drugs 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 4
- 238000012650 click reaction Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- KVYKDNGUEZRPGJ-UHFFFAOYSA-N 1-Aminohydantoin Chemical compound NN1CC(=O)NC1=O KVYKDNGUEZRPGJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940091173 hydantoin Drugs 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 201000005947 Carney Complex Diseases 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005553 drilling Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical group FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LXIBJKCYJYSXRU-UHFFFAOYSA-N C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O.[Ni].[Na].[Na] Chemical compound C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O.[Ni].[Na].[Na] LXIBJKCYJYSXRU-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- JZDQXPACWMCLKT-UHFFFAOYSA-N [Ni].[Sn].[Au] Chemical compound [Ni].[Sn].[Au] JZDQXPACWMCLKT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to the technical field of corrosion-resistant copper terminals, in particular to a corrosion-resistant copper terminal and a processing technology thereof. Step 1: sequentially carrying out cold heading forming, turning and CNC processing on the copper material to obtain a copper terminal matrix; step 2: activating the surface of a copper terminal matrix to obtain a copper terminal matrix A; and then sequentially electrodepositing a nickel-graphene layer, a gold-tin layer and a gold-copper-cobalt-graphene quantum dot layer on the surface of the copper terminal matrix A to obtain the corrosion-resistant copper terminal. In the scheme, a nickel-graphene layer, a gold-tin layer and a gold-copper-cobalt-graphene quantum dot layer are electrodeposited on a copper terminal substrate in sequence to form a three-layer composite plating layer; on the basis of ensuring the low resistance of the copper terminal, the corrosion resistance and the wear resistance of the copper terminal are effectively enhanced.
Description
Technical Field
The invention relates to the technical field of corrosion-resistant copper terminals, in particular to a corrosion-resistant copper terminal and a processing technology thereof.
Background
The terminal block is an electrical connector for connecting a wire to an electrical device; copper is a material with low resistance and high conductivity compared with other metal materials, so that the copper terminal can reduce the electric energy loss to the greatest extent and is most widely applied.
In recent years, under the technological progress and the field expansion, the requirements of electrical equipment are higher and higher, and therefore, the quality requirements on copper terminals are also higher and higher. In the prior art, the corrosion resistance of the copper terminal is improved by sequentially plating a nickel layer and a gold layer on the surface of the copper terminal, and the plating layer still has the following problems: firstly, corrosion resistance still needs to be further improved, although the nickel plating layer is used for blocking the heat diffusion of copper atoms before gold plating in the prior art, the blocking property is limited, and the nickel layer also can be outwards heat-diffused, so that the bonding strength of a plating layer is weakened, the corrosion resistance is reduced, and the service life is shortened. Secondly, the wear resistance needs to be further enhanced, and poor contact of the terminal in the later period is prevented; in the prior art, gold is softer, a single gold-plated layer is higher in cost and lower in wear resistance, and in the prior art, single copper, cobalt and nickel are generally introduced for forming an alloy plating layer, but brittleness is caused to influence current efficiency, or surface wear resistance is reduced, or interface performance of the alloy layer is poor to influence corrosion resistance.
In summary, the problems are solved, the corrosion resistance and the wear resistance are improved on the basis of effectively ensuring low resistance, and the corrosion-resistant copper terminal is prepared and has important significance in prolonging the service life.
Disclosure of Invention
The invention aims to provide a corrosion-resistant copper terminal and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
A processing technology of a corrosion-resistant copper terminal comprises the following steps:
step 1: sequentially carrying out cold heading forming, turning and CNC processing on the copper material to obtain a copper terminal matrix;
Step 2: activating the surface of a copper terminal matrix to obtain a copper terminal matrix A; and then sequentially electrodepositing a nickel-graphene layer, a gold-tin layer and a gold-copper-cobalt-graphene quantum dot layer on the surface of the copper terminal matrix A to obtain the corrosion-resistant copper terminal.
More optimally, in the cold heading forming process, an oil pressure cold heading die is used, and the stamping speed is 8-12 Pcs/min; in the turning process, the rotating speed of the main shaft is 1200-2000 r/min, and the processing speed is 50-140 s/Pcs; in the CNC machining process, the rotating speed of the main shaft is 5500-6500 r/min, and the machining speed is 100-160 s/Pcs.
More optimally, the surface activation process comprises the following steps: and (3) placing the copper terminal matrix in a phytic acid solution with the concentration of 5-6wt% for activation for 1-2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A.
More optimally, in the technical process of electrodeposition, the specific steps are as follows:
(1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 8-10 mT, setting a cathode current density to be 7-9A/dm 2 at a temperature of 45-50 ℃, performing electrodeposition for 1-2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B;
(2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2-3 mA/cm 2 at 40-45 ℃, electrodepositing for 2-4 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C;
(3) And placing the copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.5-1A/dm 2 at 40-60 ℃, electrodepositing a 6-10 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain the corrosion-resistant copper terminal.
More preferably, the nickel-graphene plating solution comprises the following components: 200-220 g/L nickel sulfate, 35-40 g/L nickel chloride, 30-32 g/L sodium acetate and 8-10 g/L modified graphene; the modified graphene is obtained by compounding thermally reduced graphene oxide and a modifier in a mass ratio of 3:1.
More preferably, the gold-tin plating solution comprises the following components: 5-7 g/L of tetrachloroauric acid, 5-7 g/L of tin dichloride, 30-32 g/L of dimethyl hydantoin, 50-52 g/L of potassium carbonate, 28-30 mg/L of phenanthroline and 10-12 mg/L of modifier.
More optimally, the gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20-22 g/L sodium gold subunit, 0.5-0.7 g/L sodium copper ethylenediamine tetraacetate, 2-3 g/L disodium cobalt ethylenediamine tetraacetate, 60-100 g/L sodium sulfite and 0.5-0.8 g/L modified graphene quantum dot; the modified graphene quantum dot is obtained by compounding graphene quantum dots and a modifier in a mass ratio of 3:1.
More optimally, the preparation method of the modifier comprises the following steps:
(1) Sequentially adding N-acetylcysteine, EDC and NHS into DMF, stirring at 40-50 ℃ for 1-2 hours under nitrogen atmosphere, adding 1-aminohydantoin-DMF solution, continuously stirring for 2-3 days, and purifying to obtain mercaptohydantoin;
(2) Mixing vinyl imidazole and butanediol diglycidyl ether, stirring and reacting for 6-8 hours at 75-80 ℃ under the protection of nitrogen, and purifying to obtain a quaternary ammonium salt compound;
(3) Sequentially adding a quaternary ammonium salt compound, mercaptohydantoin, gamma-mercaptopropyl triethoxysilane, an initiator and a polymerization inhibitor into tetrahydrofuran, carrying out a room-temperature click reaction for 1-2 hours under the condition of 100-120 mW/cm 2, and purifying to obtain the modifier.
The modifier is based on quaternary ammonium salt compound, and is grafted with mercapto hydantoin and gamma-mercapto propyl triethoxy silane through the click reaction of vinyl and mercapto; therefore, the modified polyurethane foam contains nitrogen-containing heterocycle, quaternary ammonium salt group, siloxane chain and sulfur bond, and can play roles of dispersing agent, complexing agent and leveling agent. At the same time, the material contains good corrosion resistance.
More optimally, in the sulfhydryl hydantoin, the mass ratio of the acetylcysteine to the 1-amino hydantoin is 1.6 (1.15-1.2); the mass ratio of the vinyl imidazole to the butanediol diglycidyl ether in the quaternary ammonium salt compound is 9.4:20; the mass ratio of the quaternary ammonium salt compound to the mercaptohydantoin to the gamma-mercaptopropyl triethoxysilane is 3 (2.7-3) to 2-2.3.
More optimally, the corrosion-resistant copper terminal is prepared by the processing technology of the corrosion-resistant copper terminal.
Compared with the prior art, the application has the following beneficial effects:
(1) In the scheme, the copper material made of the C110 material has good plasticity, so that the cold heading forming and oil pressure forging die is used, and the unit consumption and the processing time of the product can be greatly reduced. Compared with direct machining (turning+CNC) forming without cold heading, the material loss is lower, and the product cost is reduced. Thus, the process unit consumption of the copper terminal matrix molding is about 84 g/PCS, and the machining time is about 348 seconds/PCS.
(2) In the scheme, a nickel-graphene layer, a gold-tin layer and a gold-copper-cobalt-graphene quantum dot layer are electrodeposited on a copper terminal substrate in sequence to form a three-layer composite plating layer; on the basis of ensuring the low resistance of the copper terminal, the corrosion resistance and the wear resistance of the copper terminal are effectively enhanced.
The nickel-graphene layer can effectively avoid the heat migration of copper atoms to the outermost layer, improve the performance of the copper terminal, and can be used as a dielectric layer to effectively improve the good adhesive force of a subsequent plating layer. The introduction of the modified graphene can promote the compactness of the nickel layer, strengthen the nickel layer, and improve the changed order through setting a static magnetic field; thereby effectively improving the conductivity, corrosion resistance and barrier property of the nickel layer.
Wherein, the gold-tin layer is used as a transition layer, which has lower hardness and good toughness; the gold-tin layer can form a gold-tin-nickel interface layer with nickel in the nickel-graphene layer, so that the thermal migration of copper and nickel is further blocked, and the performance is improved; meanwhile, compared with the direct plating of the outer layer, the interlayer binding force of the gold-copper-cobalt-graphene quantum dot layer is improved effectively, so that the overall connection reliability is improved; however, the deposition time of the layer needs to be set, and the long deposition time can increase the interface thickness, thereby increasing the resistance and reducing the electrical performance and reliability.
The gold-copper-cobalt-graphene quantum dot layer is used as an outer layer, and compared with binary alloys such as gold copper, gold-cobalt and the like, the low element content can cause low hardness and poor wear resistance of the outer layer; the multielement outer layer effectively improves the microhardness, so that the wear resistance is improved, and meanwhile, in the scheme, compared with the nickel, the cobalt is introduced, so that the influence on the electrical performance is smaller.
Wherein, the nickel-graphene layer is introduced with modified graphene, which is obtained by thermally reducing graphene oxide and modifying the graphene oxide by a modifier, and compared with common graphene oxide, the nickel-graphene layer is introduced with better electrical property and corrosion resistance; and the introduction of the modifier can improve the flatness of the nickel-graphene layer, so that the roughness of the plating layer is optimized, and a foundation is laid for the subsequent plating layer. Similarly, the modified graphene quantum dots are introduced into the gold-copper-cobalt-graphene quantum dot layer, the gold-copper-cobalt-graphene quantum dot layer is prepared by modifying the graphene quantum dots with a modifier, the surface wear resistance is promoted by introducing the graphene quantum dots, and meanwhile, the copper terminal after plating has better electrical property and corrosion resistance; the modifier improves the flatness and compactness of the coating. The modifier is also introduced into the gold-tin layer, and the modifier is introduced into the gold-tin layer, so that the gold-tin layer can be cooperated with phenanthroline and dimethyl hydantoin to promote refinement; and at the same time, under the current density, the orientation of gold in the (110) plane in the gold-tin layer is increased.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
Fig. 1 is a schematic view of a copper terminal base body according to the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following parts are by mass; the purchasing manufacturers of all the raw materials involved in the present invention include, without any particular limitation: in the following examples, the brands of graphene quantum dots are north family nanometers; the open sea of the graphene oxide is screened; the sodium acetate is sodium acetate trihydrate, the nickel chloride is nickel chloride hexahydrate, the nickel sulfate is nickel sulfate heptahydrate, the CAS number of dimethyl hydantoin is 77-71-4, the CAS number of phenanthroline is 66-71-7, the CAS number of sodium copper ethylenediamine tetraacetate is 14025-12-1, the CAS number of disodium cobalt ethylenediamine tetraacetate is 15137-09-4, and the CAS number of sodium sulfite is 7757-83-7, all of which are commercially available.
Preparation of the modifier: (1) Sequentially adding 1.6 parts of N-acetylcysteine, 2 parts of EDC (carbodiimide) and 1 part of NHS (N-hydroxysuccinimide) into 1 part of DMF (N, N-dimethylformamide), stirring for 2 hours at 45 ℃ under nitrogen atmosphere, adding 1-aminohydantoin-DMF solution (1.16 parts of 1-aminohydantoin and 10 parts of DMF), continuously stirring for 3 days, and purifying to obtain mercaptohydantoin; (2) 9.4 parts of vinyl imidazole and 20 parts of butanediol diglycidyl ether are mixed, stirred and reacted for 6 hours at 75 ℃ under the protection of nitrogen, and purified to obtain a quaternary ammonium salt compound; (3) 3 parts of quaternary ammonium salt compound, 3 parts of mercaptohydantoin, 2 parts of gamma-mercaptopropyl triethoxysilane, 0.02 part of AIBN initiator and 0.01 part of polymerization inhibitor hydroquinone are sequentially added into 25 parts of tetrahydrofuran, and the mixture is subjected to room temperature click reaction for 1.5 hours under the condition of 120mW/cm 2, and then the mixture is purified to obtain the modifier.
The preparation method of the modified graphene quantum dot comprises the following steps: sequentially adding 3 parts of graphene quantum dots and 1 part of modifier into 10 parts of 50wt% ethanol water solution, stirring for 5 hours at 50 ℃, filtering, and freeze-drying to obtain modified graphene quantum dots;
The preparation method of the modified graphene comprises the following steps: (1) Dispersing 10 parts of graphene oxide in 20 parts of deionized water by ultrasonic, adding 1.5 parts of hydrazine hydrate, and heating at 95 ℃ for 24 hours; washing and drying, and calcining the graphene in an argon atmosphere at 850 ℃ for 15 minutes to obtain thermally reduced graphene oxide; (2) 3 parts of thermally reduced graphene oxide and 1 part of thermally reduced graphene oxide are sequentially added into 10 parts of 50wt% ethanol water solution, stirred for 5 hours at 50 ℃, filtered and freeze-dried to obtain modified graphene.
Example 1: a processing technology of a corrosion-resistant copper terminal comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 10mT, setting cathode current density to be 8A/dm 2 at 45 ℃, electrodepositing for 1.5 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2.5mA/cm 2 at 40 ℃, electrodepositing for 3 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (3) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.8A/dm 2 at 50 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 220g/L nickel sulfate, 35g/L nickel chloride, 30g/L sodium acetate and 10g/L modified graphene;
The gold-tin plating solution comprises the following components: 6g/L of tetrachloroauric acid, 6g/L of tin dichloride, 30g/L of dimethyl hydantoin, 52g/L of potassium carbonate, 30mg/L of phenanthroline and 12mg/L of modifier;
the gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20g/L sodium gold subunit, 0.6g/L sodium copper ethylenediamine tetraacetate, 2.5g/L disodium cobalt ethylenediamine tetraacetate, 80g/L sodium sulfite and 0.6g/L modified graphene quantum dot.
Example 2: a processing technology of a corrosion-resistant copper terminal comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 10mT, setting a cathode current density to be 7A/dm 2 at a temperature of 45 ℃, electrodepositing for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 3mA/cm 2 at 45 ℃, electrodepositing for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (3) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 1A/dm 2 at 40 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 200g/L nickel sulfate, 40g/L nickel chloride, 32g/L sodium acetate and 10g/L modified graphene;
The gold-tin plating solution comprises the following components: 5g/L of tetrachloroauric acid, 5g/L of tin dichloride, 30g/L of dimethyl hydantoin, 50g/L of potassium carbonate, 28mg/L of phenanthroline and 10mg/L of modifier;
the gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20-22 g/L sodium gold subunit, 0.7g/L sodium copper ethylenediamine tetraacetate, 3g/L disodium cobalt ethylenediamine tetraacetate, 100g/L sodium sulfite and 0.5g/L modified graphene quantum dot.
Example 3: a processing technology of a corrosion-resistant copper terminal comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 8mT, setting a cathode current density to be 9A/dm 2 at 50 ℃, electrodepositing for 1 minute, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2mA/cm 2 at 40 ℃, electrodepositing for 4 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (3) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.5A/dm 2 at 60 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 220g/L nickel sulfate, 35g/L nickel chloride, 30g/L sodium acetate and 8g/L modified graphene;
the gold-tin plating solution comprises the following components: 7g/L of tetrachloroauric acid, 7g/L of tin dichloride, 32g/L of dimethyl hydantoin, 52g/L of potassium carbonate, 30mg/L of phenanthroline and 12mg/L of modifier;
The gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20g/L sodium gold subunit, 0.5g/L sodium copper ethylenediamine tetraacetate, 2g/L disodium cobalt ethylenediamine tetraacetate, 60g/L sodium sulfite and 0.5g/L modified graphene quantum dot.
Comparative example 1: no gold-tin layer was provided, and the rest was the same as in example 1; the method comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 10mT, setting cathode current density to be 8A/dm 2 at 45 ℃, electrodepositing for 1.5 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing a copper terminal matrix B in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.8A/dm 2 at 50 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 220g/L nickel sulfate, 35g/L nickel chloride, 30g/L sodium acetate and 10g/L modified graphene;
the gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20g/L sodium gold subunit, 0.6g/L sodium copper ethylenediamine tetraacetate, 2.5g/L disodium cobalt ethylenediamine tetraacetate, 80g/L sodium sulfite and 0.6g/L modified graphene quantum dot.
Comparative example 2: the gold-tin layer deposition time was increased, the remainder being the same as in example 1; the method comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 10mT, setting cathode current density to be 8A/dm 2 at 45 ℃, electrodepositing for 1.5 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2.5mA/cm 2 at 40 ℃, electrodepositing for 8 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (3) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.8A/dm 2 at 50 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 220g/L nickel sulfate, 35g/L nickel chloride, 30g/L sodium acetate and 10g/L modified graphene;
The gold-tin plating solution comprises the following components: 6g/L of tetrachloroauric acid, 6g/L of tin dichloride, 30g/L of dimethyl hydantoin, 52g/L of potassium carbonate, 30mg/L of phenanthroline and 12mg/L of modifier;
the gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20g/L sodium gold subunit, 0.6g/L sodium copper ethylenediamine tetraacetate, 2.5g/L disodium cobalt ethylenediamine tetraacetate, 80g/L sodium sulfite and 0.6g/L modified graphene quantum dot.
Comparative example 3: all of the modifiers in the scheme were replaced with gamma-mercaptopropyl triethoxysilane, the remainder being the same as in example 1.
Comparative example 4: the gold-copper-cobalt-graphene quantum dot plating solution is prepared by replacing cobalt with nickel; the remainder was the same as in example 1; the method comprises the following steps:
Step 1: using an oil pressure cold heading die to perform cold heading forming on the C1100 copper material, wherein stamping oil is KD2160 cold heading forming oil, and the stamping speed is 10 Pcs/min; turning at the next time when the rotating speed of the main shaft is 2000r/min (turning the outer circle) and 1200r/min (drilling) and the processing speed is 135 s/Pcs; turning twice under the condition that the rotating speed of the main shaft is 2000r/min and the processing speed is 55 s/Pcs; the next CNC machining is performed at the machining speed of 155s/Pcs under the condition that the rotating speed of the main shaft is 6000 r/min; performing secondary CNC processing under the condition that the rotating speed of a main shaft is 6000r/min and the processing speed is 105s/Pcs to obtain a copper terminal matrix;
Step 2: placing the copper terminal matrix in a phytic acid solution with the weight percent of 5 to activate for 2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A; the following electrodeposition process was then performed on copper terminal substrate a: (1) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 10mT, setting cathode current density to be 8A/dm 2 at 45 ℃, electrodepositing for 1.5 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (2) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2.5mA/cm 2 at 40 ℃, electrodepositing for 3 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (3) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.8A/dm 2 at 50 ℃, electrodepositing a 6 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
In the technical scheme of the application, the nickel-graphene plating solution comprises the following components: 220g/L nickel sulfate, 35g/L nickel chloride, 30g/L sodium acetate and 10g/L modified graphene;
The gold-tin plating solution comprises the following components: 6g/L of tetrachloroauric acid, 6g/L of tin dichloride, 30g/L of dimethyl hydantoin, 52g/L of potassium carbonate, 30mg/L of phenanthroline and 12mg/L of modifier;
The gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20g/L sodium gold subunit, 0.6g/L sodium copper ethylenediamine tetraacetate, 2.5g/L disodium nickel ethylenediamine tetraacetate, 80g/L sodium sulfite and 0.6g/L modified graphene quantum dot.
Performance test: (1) Using a Vickers hardness tester, detecting microhardness of the coating under the load of 25 g; (2) Detecting the resistivity of the plating layer according to a resistivity test method; (3) The saturated calomel electrode is used as a reference electrode, the platinum electrode is used as an auxiliary electrode, and corrosion resistance test is carried out in 3.5wt% sodium chloride solution, and the scanning speed is 1mV/s; the data obtained are shown in the following table:
| Sample of | Microhardness (HV) | Resistivity (μΩ cm) | Corrosion current Density (μA/mm 2) |
| Example 1 | 318.5 | 1.80 | 0.668 |
| Example 2 | 316.8 | 1.82 | 0.679 |
| Example 3 | 318.1 | 1.80 | 0.685 |
| Comparative example 1 | 314.7 | 1.81 | 0.721 |
| Comparative example 2 | 312.8 | 1.87 | 0.698 |
| Comparative example 3 | 309.5 | 1.85 | 0.729 |
| Comparative example 4 | 302.7 | 1.86 | 0.703 |
Conclusion: the data in the table show that in the scheme, a nickel-graphene layer, a gold-tin layer and a gold-copper-cobalt-graphene quantum dot layer are sequentially electrodeposited on a copper terminal substrate to form a composite plating layer; on the basis of ensuring the low resistance of the copper terminal, the corrosion resistance and the wear resistance of the copper terminal are effectively enhanced. The data of comparative examples 1-2 show the importance of the gold-tin layer arrangement, which can effectively improve the plating performance, thereby improving the corrosion resistance; meanwhile, the electrodeposition time of the layer is too long, so that the thickness is increased, and the electrical performance is reduced. The data of comparative example 3 shows that the introduction of the modifier improves the quality of the coating. The data of comparative example 4 shows that the introduction of cobalt can reduce the impact on the electrical properties of the coating compared to nickel, while improving the surface hardness and wear resistance.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A processing technology of a corrosion-resistant copper terminal is characterized in that: the method comprises the following steps:
step1: sequentially carrying out cold heading forming and machining on the copper material to obtain a copper terminal matrix;
Step 2: (1) Activating the surface of a copper terminal matrix to obtain a copper terminal matrix A; (2) Placing a copper terminal matrix A in a nickel-graphene plating solution, setting a static magnetic field to be 8-10 mT, setting a cathode current density to be 7-9A/dm 2 at a temperature of 45-50 ℃, performing electrodeposition for 1-2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix B; (3) Placing the copper terminal matrix B in a gold-tin plating solution, setting the cathode current density to be 2-3 mA/cm 2 at 40-45 ℃, electrodepositing for 2-4 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix C; (4) Placing a copper terminal matrix C in gold-copper-cobalt-graphene quantum dot plating solution, setting cathode current density to be 0.5-1A/dm 2 at 40-60 ℃, electrodepositing a 6-10 mu m gold-copper-cobalt-graphene quantum dot layer, washing with water, and drying with nitrogen to obtain a corrosion-resistant copper terminal;
The nickel-graphene plating solution comprises the following components: 200-220 g/L nickel sulfate, 35-40 g/L nickel chloride, 30-32 g/L sodium acetate and 8-10 g/L modified graphene; the modified graphene is obtained by compounding thermally reduced graphene oxide and a modifier in a mass ratio of 3:1;
The gold-tin plating solution comprises the following components: 5-7 g/L of tetrachloroauric acid, 5-7 g/L of tin dichloride, 30-32 g/L of dimethyl hydantoin, 50-52 g/L of potassium carbonate, 28-30 mg/L of phenanthroline and 10-12 mg/L of modifier;
The gold-copper-cobalt-graphene quantum dot plating solution comprises the following components: 20-22 g/L sodium gold subunit, 0.5-0.7 g/L sodium copper ethylenediamine tetraacetate, 2-3 g/L disodium cobalt ethylenediamine tetraacetate, 60-100 g/L sodium sulfite and 0.5-0.8 g/L modified graphene quantum dot; the modified graphene quantum dot is obtained by compounding graphene quantum dots and a modifier in a mass ratio of 3:1.
2. The process for manufacturing a corrosion-resistant copper terminal according to claim 1, wherein: the surface activation process comprises the following steps: and (3) placing the copper terminal matrix in a phytic acid solution with the concentration of 5-6wt% for activation for 1-2 minutes, washing with water, and drying with nitrogen to obtain a copper terminal matrix A.
3. A process for manufacturing a corrosion-resistant copper terminal according to any one of claims 1 to 2, wherein: the preparation method of the modifier comprises the following steps:
(1) Sequentially adding N-acetylcysteine, EDC and NHS into DMF, stirring at 40-50 ℃ for 1-2 hours under nitrogen atmosphere, adding 1-aminohydantoin-DMF solution, continuously stirring for 2-3 days, and purifying to obtain mercaptohydantoin;
(2) Mixing vinyl imidazole and butanediol diglycidyl ether, stirring and reacting for 6-8 hours at 75-80 ℃ under the protection of nitrogen, and purifying to obtain a quaternary ammonium salt compound;
(3) Sequentially adding a quaternary ammonium salt compound, mercaptohydantoin, gamma-mercaptopropyl triethoxysilane, an initiator and a polymerization inhibitor into tetrahydrofuran, carrying out room-temperature click reaction for 1-2 hours under the condition of 100-120 mW/cm < 2 >, and purifying to obtain the modifier.
4. A process for manufacturing a corrosion-resistant copper terminal according to claim 3, wherein: in the sulfhydryl hydantoin, the mass ratio of the acetylcysteine to the 1-amino hydantoin is 1.6:1.15-1.2; the mass ratio of the vinyl imidazole to the butanediol diglycidyl ether in the quaternary ammonium salt compound is 9.4:20; the mass ratio of the quaternary ammonium salt compound to the mercaptohydantoin to the gamma-mercaptopropyl triethoxysilane is 3:2.7-3:2-2.3.
5. A corrosion-resistant copper terminal according to any one of claims 1 to 4.
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| CN109137016A (en) * | 2018-09-30 | 2019-01-04 | 湖州金业电镀有限公司 | A kind of alkalinity graphene Zn-Fe alloy electroplating liquid, preparation method and electroplating technology |
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