CN110158129B - Pre-penetrant composition, pre-penetrant, copper plating pretreatment method, and cyanide-free copper plating method - Google Patents
Pre-penetrant composition, pre-penetrant, copper plating pretreatment method, and cyanide-free copper plating method Download PDFInfo
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- CN110158129B CN110158129B CN201910445567.2A CN201910445567A CN110158129B CN 110158129 B CN110158129 B CN 110158129B CN 201910445567 A CN201910445567 A CN 201910445567A CN 110158129 B CN110158129 B CN 110158129B
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- complexing agent
- copper plating
- penetrant
- cyanide
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- 238000007747 plating Methods 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 239000010949 copper Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002203 pretreatment Methods 0.000 title claims abstract description 9
- -1 pre-penetrant Substances 0.000 title description 3
- 239000008139 complexing agent Substances 0.000 claims abstract description 80
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 35
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 230000000149 penetrating effect Effects 0.000 claims abstract description 25
- 229940095064 tartrate Drugs 0.000 claims abstract description 23
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 22
- 229940050410 gluconate Drugs 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003890 succinate salts Chemical group 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 239000002357 osmotic agent Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 24
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000005187 foaming Methods 0.000 abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 28
- 238000009713 electroplating Methods 0.000 description 22
- 238000004512 die casting Methods 0.000 description 16
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 5
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 5
- 239000000176 sodium gluconate Substances 0.000 description 5
- 235000012207 sodium gluconate Nutrition 0.000 description 5
- 229940005574 sodium gluconate Drugs 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 150000003892 tartrate salts Chemical class 0.000 description 2
- HSXKMKJYFOZAIV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;copper Chemical compound [Cu].OCCN(CCO)CCO HSXKMKJYFOZAIV-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 description 1
- CUCLPTNYJBVNOG-UHFFFAOYSA-L [Cu+2].C(=O)([O-])C(O)C(O)C(=O)[O-].C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound [Cu+2].C(=O)([O-])C(O)C(O)C(=O)[O-].C(CC(O)(C(=O)O)CC(=O)O)(=O)O CUCLPTNYJBVNOG-UHFFFAOYSA-L 0.000 description 1
- GVJNTKYYZXDYAH-UHFFFAOYSA-K [Cu+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O Chemical compound [Cu+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O GVJNTKYYZXDYAH-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a pre-penetrant composition, a pre-penetrant, a copper plating pretreatment method and a cyanide-free copper plating method, wherein the pre-penetrant composition comprises a first complexing agent, a second complexing agent and a third complexing agent; the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol; the weight-volume ratio of the first complexing agent to the second complexing agent to the third complexing agent is (15-30) g, (10-35) g, (1-4.5) mL. The invention adopts the pre-penetrating agent composition for soaking pretreatment, so that the complexing agent penetrates into pores and cracks on the surface of the workpiece, copper ions can be well complexed in the subsequent cyanide-free copper plating process, a copper plating layer is covered in the defects of tiny bubbles, cracks, pinholes and the like which are invisible to the naked eye on the surface of the workpiece to be plated, the problem of foaming caused by the pores on the surface of the workpiece can be solved, and the binding force between the cyanide-free copper plating layer and an alloy matrix is improved.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a pre-penetrating agent composition, a pre-penetrating agent, a copper plating pretreatment method and a cyanide-free copper plating method.
Background
The zinc alloy has good casting performance, is excellent casting alloy and has more superiority when being used for casting workpieces with complex shapes and high precision. In the traditional zinc alloy electroplating process, cyanide copper plating is used as a pre-copper plating process, and has the advantages of good binding force, good dispersing capacity, fine crystallization, low porosity, stable plating solution, simple maintenance and the like from the technical point of view. However, cyanide is a highly toxic chemical, the death causing amount of the cyanide is only 0.005g, and cyanide copper plating solution can release highly toxic cyanide in the electroplating process, so that the cyanide copper plating solution has great harm to the health of electroplating workers and has great potential safety hazard.
There has been a long-standing effort to replace the cyanide copper plating process. Heretofore, cyanide-free alkaline copper plating processes are of various types, including pyrophosphate copper plating, ethylenediamine copper plating, citrate copper plating, tartrate copper plating, triethanolamine copper plating, EDTA copper plating, gluconate copper plating, fluoroborate copper plating, sulfamate copper plating, and mixed complexing agent system copper plating, such as: citric acid-tartrate copper plating, EDTA-citric acid-tartrate copper plating, and the like have been reported. However, the cyanide-free alkaline copper plating process of the above system generally has the problems of low deposition rate, poor bonding force and the like, and the problem of foaming of a coating after baking cannot be completely solved in electroplating of zinc alloy die castings, so that cyanide copper plating cannot be generally replaced. The cyanide-free alkaline copper plating of an HEDP (hydroxyethylidene diphosphate) system is proved by practice to be capable of obtaining better bonding force on aluminum alloy parts and iron parts, in the aspect of zinc alloy die casting, the problem of copper replacement is solved by technological improvements, such as reduction of copper content concentration in plating solution, reduction of working temperature of the plating solution, electrification of a lower tank, large-current electroplating in a short time after the lower tank and the like, the plating performance reaches the cyanide copper plating level, but the process can only be applied to a small part of zinc alloy die castings with good die casting quality, the die-casting quality depends on the reasonability of the design of a die, the proportion of metal components in the zinc alloy, the content of impurities, the operating conditions of the die-casting process and the like, most of zinc alloy die-casting pieces have common quality, and particularly the zinc alloy die-casting pieces mixed with a certain amount of reclaimed materials still cannot replace cyanide copper plating by cyanide-free alkaline copper plating.
Therefore, cyanide copper plating still exists in a great amount in the electroplating process of zinc alloy die castings, and is particularly more common in small and medium-sized enterprises, and a process for electroplating zinc alloy by cyanide-free alkaline copper plating solution capable of replacing cyanide copper plating is urgently needed.
Disclosure of Invention
Accordingly, there is a need for a pre-penetrant composition that can improve the bonding force between a copper plating layer and an alloy substrate, and can realize industrial cyanide-free copper plating.
A pre-penetrant composition comprising a first complexing agent, a second complexing agent, and a third complexing agent;
the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol;
the weight-volume ratio of the first complexing agent to the second complexing agent to the third complexing agent is (15-30) g, (10-35) g, (1-4.5) mL.
According to the pre-penetrating agent composition, a specific complexing agent component is selected, and a plurality of complexing agents are matched, so that when a workpiece to be plated is subjected to penetration treatment, complexing agent molecules can fully penetrate into tiny bubbles, cracks, pinholes and other defects invisible to the naked eye on the surface of the workpiece, and therefore in the subsequent cyanide-free copper plating process, the complexing agents can well complex copper ions in a plating solution, the copper ions fully cover the cracks and pores on the surface of the workpiece to be plated to form a copper plating layer, the binding force of the copper plating layer and a substrate of the workpiece to be plated is improved, and a base stone is provided for industrialization of cyanide-free copper plating.
In one embodiment, the second complexing agent is a mixture of tartrate and gluconate, and the weight ratio of the tartrate to the gluconate is (5-20) to (5-25).
The invention also provides a pre-penetrant, which comprises 15 g/L-30 g/L of a first complexing agent, 10 g/L-35 g/L of a second complexing agent and 1 mL/L-4.5 mL/L of a third complexing agent;
the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol.
In one embodiment, in the pre-penetrant, the concentration of tartrate is 10 g/L-20 g/L, and the concentration of gluconate is 0 g/L-25 g/L.
In one embodiment, in the pre-penetrant composition, the concentration of the tartrate salt is 10 g/L-20 g/L, and the concentration of the gluconate salt is 0 g/L-25 g/L.
In one embodiment, in the pre-penetrant composition, the concentration of tartrate is 0-20 g/L, and the concentration of gluconate is 10-25 g/L.
In one embodiment, in the pre-penetrant composition, the concentration of the tartrate salt is 5 g/L-20 g/L, and the concentration of the gluconate salt is 5 g/L-25 g/L.
In one embodiment, the concentration of the third complexing agent in the pre-penetrant is 1mL/L to 3.5 mL/L.
In one embodiment, in the pre-penetrant, the concentration of ethylenediamine is 0-2.5 mL/L, the concentration of glycerin is 0-2 mL/L, and at least one of the contents of ethylenediamine and glycerin is not zero.
In one embodiment, the pH value of the pre-penetrating agent is 8-14.
In one embodiment, the pH adjusting agent is selected from at least one of dipotassium hydrogen phosphate and potassium carbonate.
The invention also aims to provide a copper plating pretreatment method, which comprises the following steps:
and soaking the workpiece to be plated by adopting the pre-penetrating agent.
In one embodiment, the temperature of the soaking treatment is 30-40 ℃, and the time is 5-20 min.
Therefore, the complexing agent can be promoted to enter pores on the surface of the workpiece to be plated by maintaining the temperature of the soaking treatment at 30-40 ℃, so that a good permeation effect can be achieved within 5-20 min.
In one embodiment, the soaking treatment is carried out under ultrasonic conditions, and the sound intensity of the ultrasonic is 200w/m2～300w/m2。
In one embodiment, the workpiece to be plated is a zinc alloy workpiece to be plated.
The invention also provides a cyanide-free copper plating method, which comprises the following steps:
soaking a workpiece to be plated by adopting the pre-penetrating agent;
and carrying out copper plating on the workpiece to be plated after the soaking treatment by adopting cyanide-free copper plating solution.
Compared with the traditional copper plating process, the method has the advantages that the pretreatment step is added before the copper plating is carried out on the workpiece to be plated, the workpiece to be plated is soaked by the pre-penetrating agent disclosed by the invention, so that the complexing agent penetrates into the defects of tiny bubbles, cracks, pinholes and the like invisible to the naked eye on the surface of the workpiece to be plated, copper ions can be well complexed in the subsequent cyanide-free copper plating process, a copper plating layer covers the pores and cracks on the surface of the workpiece to be plated, the problem of foaming caused by the surface pores of a zinc alloy die casting can be solved, the binding force of a cyanide-free copper plating layer and a zinc alloy matrix is improved, and the electroplating requirement of cyanide-free copper plating is. Moreover, the cyanide-free copper plating method avoids using cyanide-containing copper plating solution, meets the requirements of environmental protection and sustainable production, and can reduce environmental pollution.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The zinc alloy matrix is composed of zinc, aluminum and a small amount of metals such as copper and magnesium, in the die-casting process, when the zinc alloy matrix is changed from a molten state to a solid state, due to different cooling solidification points, the surface is easy to generate component segregation phenomenon, particularly, the adult segregation phenomenon on the surface of a workpiece is aggravated for some zinc alloy die-casting parts mixed with reclaimed materials, and the matrix is provided with tiny bubbles, cracks, pinholes and other defects which are invisible to the naked eye when the die-casting is molded, so that the surface of the die-casting part is mostly of a porous structure. After the workpiece is polished, polishing wax is easily embedded into the fine pores and is difficult to remove, and after pretreatment, pretreatment working fluid permeates into the pores or bubbles are generated at the pore openings due to surface tension, so that current cannot be introduced into the pores. The cyanide copper plating solution mainly comprises a copper cyanide complex and a certain amount of free cyanide, and the cyanide ions are small and have strong permeability and complexing ability, so that the copper cyanide complex can enter pores on the surface of a workpiece and form a covering copper plating layer in the pores, and the binding force of the plating layer is ensured after subsequent electroplating and baking. The complexing agent molecules in the existing cyanide-free alkaline copper plating solution are larger than cyanide ions, and the penetration capability of a product obtained by complexing copper and the complexing agent is reduced due to the steric hindrance effect, so that the product cannot penetrate into the pores and form a copper plating layer.
In order to solve the problems, through a great deal of research, the inventor of the application provides a pre-penetrant composition, which is used for carrying out copper plating pretreatment on a workpiece to be plated, can improve the penetration capability of cyanide-free copper plating solution, improve the binding force between a copper plating layer and an alloy matrix, and can realize an industrialized zinc alloy cyanide-free copper plating method.
A pre-penetrant composition comprising a first complexing agent, a second complexing agent, and a third complexing agent;
wherein the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol; the weight-volume ratio of the first complexing agent to the second complexing agent to the third complexing agent is (15-30) g, (10-35) g, (1-4.5) mL.
Specifically, the succinate can be potassium succinate, sodium succinate, etc.; the tartrate can be potassium sodium tartrate, potassium tartrate or sodium tartrate; the gluconate can be sodium gluconate or potassium gluconate.
In one embodiment, the second complexing agent is a mixture of tartrate and gluconate salts.
In one embodiment, the weight ratio of tartrate to gluconate is (5-20) to (5-25).
Another embodiment of the invention provides a pre-penetrant comprising 15g/L to 30g/L of a first complexing agent, 10g/L to 35g/L of a second complexing agent, and 1mL/L to 4.5mL/L of a third complexing agent;
the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol.
It is worth to be noted that the concentrations of the components in the pre-penetrating agent are the final concentrations of the pre-penetrating agent used for pre-penetrating the workpiece to be plated, and the same is applied below.
The specific product form can comprise various forms, such as a pre-penetrant composition with a first complexing agent, a second complexing agent and a third complexing agent existing in the original state of raw materials, and then the pre-penetrant composition is dissolved in water when in use to obtain a pre-penetrant with a final concentration meeting the requirement; or dissolving the first complexing agent, the second complexing agent and the third complexing agent in water to obtain concentrated solution with certain concentration, and then diluting the concentrated solution when in use to obtain the pre-penetrant composition solution with final concentration meeting the requirement.
For example, the pre-penetrant comprises 30-60 g/L potassium succinate, 20-40 g/L potassium sodium tartrate, 0-50 g/L sodium gluconate and 2.5-7 mL/L third complexing agent, and when the pre-penetrant is used, the pre-penetrant is diluted by 2 times to obtain a pre-penetrant solution comprising 15-30 g/L potassium succinate, 10-20 g/L potassium sodium tartrate, 0-25 g/L sodium gluconate and 1-4.5 mL/L third complexing agent.
The pre-penetrant comprises 150 g/L-300 g/L potassium succinate, 50 g/L-200 g/L potassium sodium tartrate, 50 g/L-250 g/L sodium gluconate and 12.5 mL/L-35 mL/L third complexing agent, and when the pre-penetrant is used, the pre-penetrant is diluted by 100 times to obtain a pre-penetrant solution comprising 15 g/L-30 g/L potassium succinate, 5 g/L-20 g/L potassium sodium tartrate, 5 g/L-25 g/L sodium gluconate and 1 mL/L-4.5 mL/L third complexing agent.
In one embodiment, the concentration of tartrate in the pre-osmotic agent is 10g/L to 20g/L and the concentration of gluconate in the pre-osmotic agent is 0g/L to 25 g/L.
In one embodiment, in the pre-osmotic agent, the concentration of tartrate is 0-20 g/L, and the concentration of gluconate is 10-25 g/L.
In one embodiment, the concentration of tartrate in the pre-osmotic agent is 5g/L to 20g/L and the concentration of gluconate in the pre-osmotic agent is 5g/L to 25 g/L.
In one embodiment, the concentration of the third complexing agent in the pre-penetrant is 1mL/L to 3.5 mL/L.
In one embodiment, the concentration of ethylenediamine is 0-2.5 mL/L, the concentration of glycerol is 0-2 mL/L, and at least one of ethylenediamine and glycerol is not zero in the pre-osmotic agent.
In one embodiment, the pH of the pre-osmotic agent is 8-14.
In one embodiment, the pH adjusting agent is selected from at least one of dipotassium hydrogen phosphate and potassium carbonate.
In one embodiment, the concentration of dipotassium hydrogen phosphate is 2g/L to 7.8g/L and the concentration of potassium carbonate is 0.25g/L to 2.5g/L in the pre-penetrant.
In another embodiment of the present invention, a copper plating pretreatment method is provided, which includes the steps of:
and soaking the workpiece to be plated by adopting the pre-penetrating agent.
In one embodiment, the temperature of the soaking treatment is 30-40 ℃ and the time is 5-20 min.
In one embodiment, the soaking treatment is carried out under ultrasonic conditions with an ultrasonic sound intensity of 200w/m2～300w/m2。
In one embodiment, the workpiece to be plated is a zinc alloy workpiece to be plated.
In one embodiment, before the step of performing the soaking treatment on the workpiece to be plated, the method further comprises the steps of performing wax removal, oil removal and activation treatment on the workpiece to be plated.
Further, hot dipping or/and ultrasonic dewaxing may be employed; hot dipping or/and ultrasonic degreasing are adopted.
In another embodiment of the present invention, there is provided a cyanide-free copper plating method including the steps of:
soaking a workpiece to be plated by adopting the pre-penetrating agent;
and (4) carrying out copper plating on the workpiece to be plated after the soaking treatment by using cyanide-free copper plating solution.
In one embodiment, the cyanide-free copper plating solution is a cyanide-free alkaline copper plating solution.
In one embodiment, after the step of copper plating the workpiece to be plated after the soaking treatment is carried out by using the cyanide-free copper plating solution, the steps of coke copper plating, semi-bright nickel plating, chromium plating, drying and the like are further included.
The following are specific examples
1. According to the dosage of each raw material component in the pre-penetrating agent composition shown in the following table 1, preparing each raw material component, adding each raw material component into pure water, dissolving, physically and uniformly mixing, and fixing the volume to 1L to obtain the pre-penetrating agent.
TABLE 1
2. The method comprises the following steps of (1) carrying out cyanide-free electroplating treatment on a zinc alloy workpiece to be plated, wherein the process flow of the treatment is as follows:
zinc alloy die-cast blank → hot dipping wax removal → ultrasonic wave wax removal → hot dipping oil → ultrasonic wave oil removal → cathode electrolysis oil removal → activation → ultrasonic wave pre-penetration → hot pure water washing → electroplating cyanide-free alkaline copper plating → electroplating pyrocopper → electroplating acid copper → electroplating semigloss nickel → electroplating bright nickel → electroplating chromium → drying.
In the ultrasonic pre-infiltration step, the pre-infiltration agents prepared in the above examples 1 to 7 and comparative examples 1 to 3 are respectively diluted into a pre-infiltration agent solution of 1000ml/L with the pH value of 8 to 14, and then the zinc alloy die-casting blank subjected to the activation treatment is soaked in the pre-infiltration agent solution for infiltration, andthe sound intensity is 200w/m2～300w/m2The temperature of the pre-penetrating agent solution is 30-40 ℃ and the penetrating time is 10 min.
And set up the comparative example 4 without cyanogen electroplating treatment of ultrasonic wave pre-infiltration process, other operation steps of the comparative example 4 are the same as the technological process of the above-mentioned treatment; comparative example 5 the treatment process of comparative example 5 was substantially the same as in examples 1 to 7 of the present invention except that cyanide copper plating was used instead of cyanide-free alkaline copper plating.
After the subsequent electroplating is performed in the examples 1-7 and the comparative examples 1-5, a thermal shock test is performed in the drying process, the binding force condition is observed, the influence of the pre-penetrating agent process on the binding force of the cyanide-free alkaline copper-plated coating and the zinc alloy matrix is judged, and the obtained results are shown in the following table 2.
TABLE 2
Note: according to the requirements of zinc alloy electroplating, foaming in a 120 ℃ thermal shock test is regarded as unqualified, and non-foaming in a 150 ℃ thermal shock test is regarded as good binding force.
The zinc alloy workpiece used in the embodiment of the invention is a 3# zinc alloy workpiece with poor die casting and loose surface, and the cyanide-free alkaline copper plating product of a certain company adopting an organic phosphonate system is adopted.
From the results in the above table 2, it can be seen that the products obtained by the cyanide-free electroplating process in the embodiments 1 to 7 of the present invention pass the 120 ℃ thermal shock test, and the zinc alloy workpiece is subjected to the penetrating treatment by using the pre-penetrating agents in the embodiments 1 to 7 before the cyanide-free alkaline copper plating process, so that the binding force between the copper plating layer and the zinc alloy substrate is improved, and the products obtained in the embodiments 1 to 5 have good binding force between the copper plating layer and the zinc alloy substrate, can achieve the effect of cyanide copper plating, can replace the cyanide copper plating process, and are industrially popularized.
And the products obtained in the comparative examples 1 to 4 are unqualified, specifically, the dosage of each complexing agent in the pre-penetrating agent in the ultrasonic pre-penetrating treatment of the comparative examples 1 to 3 is different from that in the embodiment, the obtained products are unqualified, the electroplating process of ultrasonic pre-penetrating is not added before the cyanide-free alkaline copper plating is electroplated in the comparative example 4, bubbles are formed on the surface of the workpiece after the workpiece is baked at 120 ℃ for 60min, and the obtained products are not qualified.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A pre-penetrant composition comprising a first complexing agent, a second complexing agent, and a third complexing agent;
the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol;
the weight-volume ratio of the first complexing agent to the second complexing agent to the third complexing agent is (15-30) g, (10-35) g, (1-4.5) mL.
2. The pre-penetrant composition of claim 1 wherein the second complexing agent is a mixture of tartrate and gluconate, and the weight ratio of tartrate to gluconate is (5-20): 5-25.
3. A pre-penetrant is characterized in that the pre-penetrant comprises 15 g/L-30 g/L of a first complexing agent, 10 g/L-35 g/L of a second complexing agent and 1 mL/L-4.5 mL/L of a third complexing agent;
the first complexing agent is succinate, the second complexing agent is at least one selected from tartrate and gluconate, and the third complexing agent is at least one selected from ethylenediamine and glycerol.
4. The pre-penetrant of claim 3 wherein the concentration of tartrate in the pre-penetrant is 10-20 g/L, and the concentration of gluconate in the pre-penetrant is 0-25 g/L;
or the concentration of the tartrate is 0-20 g/L, and the concentration of the gluconate is 10-25 g/L;
or in the pre-penetrant, the concentration of the tartrate is 5 g/L-20 g/L, and the concentration of the gluconate is 5 g/L-25 g/L.
5. The pre-osmotic agent according to claim 3, wherein the concentration of ethylenediamine is 0 to 2.5mL/L, the concentration of glycerin is 0 to 2mL/L, and at least one of the contents of ethylenediamine and glycerin is not zero.
6. The agent according to any one of claims 3 to 5, wherein the pH of the agent is 8 to 14.
7. A copper plating pretreatment method is characterized by comprising the following steps:
soaking a workpiece to be plated by using the pre-penetrating agent as defined in any one of claims 3 to 6.
8. The copper plating pretreatment method according to claim 7, wherein the immersion treatment is performed at a temperature of 30 to 40 ℃ for 5 to 20 minutes.
9. The copper plating pretreatment method according to claim 8, wherein the immersion treatment is performed under ultrasonic conditions, and the sound intensity of the ultrasonic is 200w/m2～300w/m2。
10. The cyanide-free copper plating method is characterized by comprising the following steps of:
soaking a workpiece to be plated by using the pre-penetrating agent as defined in any one of claims 3 to 5;
and carrying out copper plating on the workpiece to be plated after the soaking treatment by adopting cyanide-free copper plating solution.
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