CN104630846A - Electroplating solution for EDTA salt cyanide-free copper plating and electroplating method - Google Patents
Electroplating solution for EDTA salt cyanide-free copper plating and electroplating method Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 238000009713 electroplating Methods 0.000 title claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 38
- 238000000576 coating method Methods 0.000 abstract description 38
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229960001484 edetic acid Drugs 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000238097 Callinectes sapidus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- ZFXTZKMYLJXJDY-UHFFFAOYSA-N copper;oxalonitrile Chemical compound [Cu].N#CC#N ZFXTZKMYLJXJDY-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 238000009736 wetting Methods 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an electroplating solution for EDTA (ethylene diamine tetraacetic acid) salt cyanide-free copper plating and an electroplating method. The electroplating solution comprises 15-25g/L Cu2(OH)2CO3, 140-170g/L EDTA, 20-40g/L diethylenetriamine and 4-8g/L nitrate. The electroplating solution provided by the invention adopts EDTA as the coordination agent and diethylenetriamine as the auxiliary coordination agent, so that the electroplating solution has good dispersion force and deep plating ability, high cathode current efficiency, and excellent performance. The coating obtained by electroplating of the electroplating solution under an alkaline condition has low porosity and good quality.
Description
Technical field
The present invention relates to the technical field of copper plating process, particularly relate to a kind of electroplate liquid and electro-plating method of edta salt cyanide-free copper electroplating.
Background technology
Copper has good electroconductibility and thermal conductivity, and comparatively soft, easy polishing, is soluble in nitric acid, is also soluble in the vitriol oil of heating, acts on very slow in hydrochloric acid and dilute sulphuric acid.Be easy in atmosphere be oxidized (especially in a heated condition), itself color and gloss will be lost after oxidation, in damp atmosphere, generating one deck ventilation breather with carbonic acid gas or oxide compound effect, when being subject to sulfide effect, brown or black thin film will be generated.
Due to the calibration of copper current potential, thus it is easy to deposit on other metal.Using copper as bottom, when using together with bright nickel and tiny crack chromium, very good corrosion stability coating can be obtained.Copper coating effectively can be protected the etch of zine pressure casting acid and alkali nickel plating solution and dissolve, and thus prevent displacement plating, and when electro-galvanizing die casting, copper is absolutely necessary as bottom.Equally, copper facing before steel part nickel plating chromium, is easily polished to very high surface luminous intensity, thus can reduce polishing and the polishing cost of some steel part.So copper coating is commonly used to the bottom as gold and silver, nickel and chromium coating.In addition, owing to having good electroconductibility, copper coating is also widely used on printed-wiring board (PWB).Copper can stop the scattering and permeating of carbon, nitrogen effectively, and the copper coating of low porosity, as a kind of blocking layer, is also widely used in nitriding and the carburization process of steel matrix part.
The covering power of cyanide electroplating plating solution and leveling ability good, coating crystallization is careful, good with the bonding force of matrix, and technology maturation, technological operation is simple, has been widely used in the bottoming coating of various metal matrix material for a long time.But the toxicity of prussiate is large, and lethal quantity is only 50mg, China has put into effect relevant decree policy and has prohibited than using prussiate plating.Thus, cyanide-free copper electroplating becomes a trend of following electro-coppering development.
The performance of existing cyanide-free copper electroplating ubiquity plating solution is not ideal enough, the technological deficiency that quality of coating is not strong, these seriously constrain cyanide-free copper electroplating industrially completely replace have cyanogen copper facing.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of electroplate liquid of edta salt cyanide-free copper electroplating, and the plating solution performance of this electroplate liquid is excellent, and quality of coating is good.
An electroplate liquid for edta salt cyanide-free copper electroplating, comprises the Cu that content is 15 ~ 25g/L
2(OH)
2cO
3, content is the edta salt of 120 ~ 160g/L, content is 20 ~ 40g/L Diethylenetriaminee (DETA) and content is the nitrate of 2 ~ 8g/L.
Wherein, described edta salt is EDETATE SODIUM and/or four sodium.
Wherein, the Cu that content is 22g/L is comprised
2(OH)
2cO
3, content is the EDETATE SODIUM of 150g/L, content is 32g/L Diethylenetriaminee (DETA) and content is the nitrate of 4g/L.
Wherein, described nitrate is ammonium nitrate.
In the technical scheme of above electroplate liquid, EDTA is selected to be coordination agent.EDTA Chinese name is ethylenediamine tetraacetic acid (EDTA).The organic complexing agent that EDTA is is matrix with aminoacetaldehyde diethyl acid groups, has six can form the atom of coordinate bond with metal ion, and namely two amino nitrogens and four complete base oxygen, and nitrogen, Sauerstoffatom have lone-pair electron, can form coordinate bond with metal ion.It can form pentacyclic huge legendary turtle compound with central ion, is the intercalating agent that a kind of coordination ability is very strong.Cupric standard potential is+0.340V, and the degree of polarization of simple copper ion plating solution is lower, and the velocity of discharge of copper is very fast.Carry out electroplating that the coating obtained is coarse, bonding force is bad according to simple salt plating solution.Add EDTA, it can form stable complexing ion with bivalent cupric ion coordination, and the better simply bivalent cupric ion of the discharge potential of complexing ion when cathodic deposition is more negative, and namely degree of polarization is larger.Thus, complexing ion electric discharge is more steady, makes the more careful smooth of coating.
Select Diethylenetriaminee (DETA) as auxiliary complexing agent.Diethylenetriaminee (DETA) is preferably Tripotassium Citrate, Trisodium Citrate or ammonium nitrate.Diethylenetriaminee (DETA) can form the complexing ion of mixed ligand body with bivalent cupric ion together with EDTA.Diethylenetriaminee (DETA) can improve the dispersive ability of plating solution, strengthens the shock absorption of plating solution, promotes anode dissolution, increases the luminance brightness of permissible current density and raising coating.Diethylenetriaminee (DETA) is ammonium nitrate more preferably.The ammonium ion that ammonium nitrate contains can improve Deposit appearance.
Select nitrate as conducting salt.Nitrate can improve the upper limit, minimizing pin hole, the service temperature reducing plating solution, the raising dispersive ability of working current density, but obviously reduces current efficiency.Nitrate is preferably ammonium nitrate, and ammonium nitrate effectively can improve the current density of allowing than adding saltpetre or SODIUMNITRATE and improve quality of coating.
Select Cu
2(OH)
2cO
3(ventilation breather) is the main salt of copper.Cu
2(OH)
2cO
3the hydroxide radical contained can maintain the alkaline environment of plating solution, and carbonate can improve the crystalline structure of coating.Compared to the main salt of copper of copper sulfate and cupric nitrate, Cu
2(OH)
2cO
3anionic impurity can not be introduced to plating solution, this is because hydroxide radical by plating solution alkaline environment required, carbonate is overflowed with the form of carbonic acid gas in acid condition.With this, avoid the decline of the excessive binding force of cladding material caused of sulfate radical and nitrate radical.
The present invention provides a kind of electro-plating method on the other hand, and it is good that the method can make to electroplate by the plating solution of excellent performance the quality of coating obtained.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, comprises the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 15 ~ 25g Cu (OH)
2cO
3, 140 ~ 170g EDTA, 25g Diethylenetriaminee (DETA) and 6g nitrate;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
Wherein, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 1 ~ 3ms, and dutycycle is 5 ~ 30%, and average current density is 1 ~ 3A/dm
2.
Wherein, in described step (2), the pH of electroplate liquid is 9 ~ 10.
Wherein, the temperature of electroplate liquid is 40 ~ 60 DEG C.
Wherein, the time of plating is 40 ~ 60min.
Wherein, in described step (2), the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 1.
In the technical scheme of above electro-plating method, monopulse rectangular wave current is defined as at t
1passing into current density in time is J
pelectric current, at t
2without passing into electric current in time, it is a kind of intermittent pulse current.Dutycycle is defined as t
1/ (t
1+ t
2), frequency is 1/(t
1+ t
2), mean current is defined as J
pt
1/ (t
1+ t
2).Compare with DC electrodeposition, thickness and the ion concentration distribution of electrostatic double layer all change; While adding electrochemical polarization, reduce concentration polarization, the direct effect of generation is, the coating that pulse plating obtains than DC electrodeposition coating evenly, crystallization is finer and closely woven.Moreover, pulse plating also has: hardness and the wear resistance of (1) coating are all high; (2) solution dispersibility and covering power good; (3) decrease the super plating of part edge, coating distributing homogeneity is good, can save plating solution consumption.
The pH value of plating solution is 11 ~ 13.This alkaline environment is on the one hand in order to make EDTA have good solvability; On the other hand, also the more important thing is, make EDTA the degree of hydrogen dissociation occur comparatively greatly, thus the chelating number of rings that raising EDTA and cupric ion form inner complex is more to improve its stability.Meanwhile, the generation that the inner complex that these stability are higher can effectively prevent copper hydroxide from precipitating, improves cathode current density efficiency.
Using the steel plate of low-carbon (LC) as negative electrode, take copper sheet as anode.Anticathode pre-treatment comprises anticathode sand papering and subsequent oil removing.This use sand papering can polish twice, and first time with flint paper such as 200 object sand paperings, can be used fine sandpaper, such as, can use WC28 abrasive paper for metallograph for the second time.This oil removing can first adopt chemical alkali liquor oil removing then to adopt the dehydrated alcohol oil removing of 95%.Wherein, chemical alkali lye consists of: 40 ~ 60g/L NaOH, 50 ~ 70g/L Na
3pO
4, 20 ~ 30g/L Na
2cO
3with 3.5 ~ 10g/LNa
2siO
3.
In the present invention, electroplate liquid stirs in energising electroplating process, and the rotating speed of stirring controls in stirring at low speed, is 100 ~ 400rpm.Stirring power reduces copper complexing ion and concentration gradient, thickness of diffusion layer and a large amount of liberation of hydrogen near electrode surface and causes the increase of cathodic area pH value, is conducive to the deposition of metal ion; Can promote that again coating thickens the uniform composition with coating continuously; The copper complexing ion that the electrolysis initial stage can also be made to produce shifts out cathodic area rapidly, thus improves quality of coating.
Plating solution of the present invention is coordination agent with EDTA, take Diethylenetriaminee (DETA) as auxiliary complexing agent, and make plating solution have good dispersion force and depth capability, cathode efficiency is high, and plating solution performance is excellent.The porosity that employing electroplates the coating of acquisition in the basic conditions at plating solution is low, and quality of coating is good.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
According to formulated electroplate liquid described in embodiment 1 ~ 6, be specially:
The quality of other feed composition is taken according to formula electronic balance.Dissolving this component raw material respectively by suitable quantity of water and mixed pours in beaker, then, adds water move to pre-determined volume, adds caustic soda and regulates pH to 11 ~ 13.
The electroplate liquid of formulated described in embodiment 1 ~ 6 and comparative example is used to carry out electric plating method:
(1) negative electrode adopts the Q235 steel plate of 10mm × 10mm × 0.2mm specification.Metalluster is exposed with the polishing of WC28 abrasive paper for metallograph to surface again after first tentatively being polished with 200 order waterproof abrasive papers by steel plate.Successively through temperature be 50 ~ 70 DEG C chemical alkali liquor oil removing, distilled water flushing, 95% dehydrated alcohol oil removing, distilled water flushing.The formula of chemistry alkali lye is 40 ~ 60g/L NaOH, 50 ~ 70g/L Na
3pO
4, 20 ~ 30g/L Na
2cO
3with 3.5 ~ 10g/L Na
2siO
3.
(2) with the copper sheet of 10mm × 10mm × 0.2mm specification for anode, by level and smooth for sand papering, deionized water rinsing and oven dry before plating.
(3) by the electroplate liquid in pretreated anode and negative electrode immersion plating groove, just plating tank is placed in thermostat water bath, and is plating tank installation electric blender, the stirring rod of electric blender is inserted in electroplate liquid.Bath temperature to be regulated makes temperature of electroplating solution maintain 40 ~ 60 DEG C, and after mechanical stirring rotating speed is adjusted to 100 ~ 400rpm, make pulse power supply, the pulsewidth of pulsed current is 1 ~ 3ms, and dutycycle is 5 ~ 30%, and average current density is 1 ~ 3A/dm
2.After 40 ~ 60min to be energised, cut off the power supply of electroplanting device.Take out steel plate, use distilled water cleaning, drying.
Embodiment 1
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 1ms, and dutycycle is 30%, and average current density is 1A/dm
2; PH is 11, and temperature is 60 DEG C, and electroplating time is 60min.
Embodiment 2
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 1ms, and dutycycle is 25%, and average current density is 1.5A/dm
2; PH is 11.5, and temperature is 55 DEG C, and electroplating time is 55min.
Embodiment 3
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 2ms, and dutycycle is 20%, and average current density is 2A/dm
2; PH is 12, and temperature is 50 DEG C, and electroplating time is 50min.
Embodiment 4
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 2ms, and dutycycle is 15%, and average current density is 3A/dm
2; PH is 13, and temperature is 45 DEG C, and electroplating time is 45min.
Embodiment 5
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 3ms, and dutycycle is 5%, and average current density is 2.5A/dm
2; PH is 12.5, and temperature is 40 DEG C, and electroplating time is 40min.
Embodiment 6
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 3ms, and dutycycle is 10%, and average current density is 2.5A/dm
2; PH is 12.5, and temperature is 50 DEG C, and electroplating time is 50min.
With reference to following methods, dispersive ability test is carried out to the plating solution of embodiment 1 ~ 6:
The dispersive ability of plating solution adopts far and near cathode method (Haring-Blue method) to measure.Measure the Hull groove that groove adopts the Hull Cell 267ml model of Kocour company of the U.S., interior dimensions is 150mm × 50mm × 70mm.Negative electrode selects thickness to be the copper sheet of 0.5mm, and working face is of a size of 50mm × 50mm; Anode is plating nickel plate with holes; Plating electric current 1A, electroplating time 30min.
The dispersive ability calculation formula of plating solution is:
Dispersive ability=[K-(the Δ M of plating solution
1/ Δ M
2)]/(K-1) (result represents with percentage);
In formula, K is negative electrode far away to the distance of anode and nearly negative electrode to the ratio of distances constant of anode, and in this test, K gets 2; Δ M
1for the increment (g) after plating on nearly negative electrode; Δ M
2for the increment (g) after plating on negative electrode far away.
With reference to following methods, covering power test is carried out to the plating solution of embodiment 1 ~ 6:
Endoporus method is adopted to measure.Negative electrode selects internal diameter 110mm, and pipe range is the copper pipe of 50mm, and one end is closed.During test, the distance of the mouth of pipe and anode is fixed on 80mm, test current 0.2A, electroplating time 30min.According to following formulae discovery:
Covering power=endoporus coating length/pipe range (result represents with percentage).
With reference to following methods, Surface flat test is carried out to the plating solution of embodiment 1 ~ 6:
Roughmeter method is adopted to test Surface flat.To Hull Cell specimen surface metal spraying emery process to be tested, make its surfaceness homogeneous, then use the RA200 type roughmeter of Shanghai Gao Zhi precision instrument company limited to measure the surfaceness of its plating front and back, according to following formulae discovery Surface flat:
The mean roughness of medullary ray before Surface flat=(mean roughness of the mean roughness-plating CB of the front medullary ray of plating)/plating, result is expressed as a percentage;
In above-mentioned formula, center line average roughness refers to the medullary ray along Hull Cell test piece width, until the mean value of low current density end METHOD FOR CONTINUOUS DETERMINATION 5 times from high electric current close end 2cm place.Originally now the groove of Hull described in method is the Hull groove of the Hull Cell 267ml model adopting Kocour company of the U.S., and the electric current of hull trough test is 0.8A//dm
2.
With reference to following methods, current efficiency test is carried out to the plating solution of embodiment 1 ~ 6:
Copper voltameter method is adopted to measure.Negative electrode to be tested and copper voltameter cleaned and dry up rear electronic scale weighing, then insert in electrodeposit groove by two negative electrodes simultaneously, be energized 10 ~ 30min, take out and clean dry up after use electronic scale weighing.According to following formulae discovery:
Current efficiency=(1.186 × cathode quality to be measured)/(electrochemical equivalent of copper voltameter quality × cathodic deposition metal to be measured) × 100%.Here, electrochemical equivalent=molar mass ÷ (depositing ions valency × 26.8), unit is g.A
-1.h
-1.In the embodiment of the present invention, cupric electrochemical equivalent is 1.186g.A
-1.h
-1.
Speed test is plated with reference to the plating solution of following methods to embodiment 1 ~ 6:
Mass method is adopted to measure sedimentation rate.Be 10 with sensitivity
-4electronic balance weighing sample plating before and after quality.By the acquisition sedimentation rate of poor quality of unit time, unit surface, press formulae discovery below:
Plating speed=(after plating before sample mass-plating sample mass)/(specimen surface to be plated long-pending × plating time).Each Data duplication is measured three times and is got its mean value.
Test with reference to the bonding force of following methods to the coating of embodiment 1 ~ 6:
The method adopting line to draw lattice measures the bonding force of coating, and being 30 degree with one cutting edge by electrodeposition cladding, converted steel draws parallel lines or the 1mm that 2mm of being separated by drawn by cutter
2square lattice.Whether the coating observing line tilts or peels off.Should master the dynamics during line, a cutter just can scratch coating, arrives matrix metal.
With reference to following methods, porosity test is carried out to the coating of embodiment 1 ~ 6:
The large young pathbreaker of porosity is directly connected to the corrosion resisting property of coating, adopts paster method to press GB5935-86 standard detection.The etchant solution that the potassium ferricyanide solution of 10g/L and the sodium chloride solution of 20g/L are tested as porosity.Operation steps is: after wiped clean of being deoiled by coating surface, is close to coating surface with the filter paper soaking into etchant solution, and the two can not have gap.Buy the fully wetting filter paper of etchant solution solution by glass stick or degreasing swab stick, supplement a solution at interval of 1min, taken off by filter paper after 5min, dry after clean with distilled water flushing, record hole is counted.Be placed on airing on cleaned glass plate, the number of number Bluepoint.Substitute into formulae discovery voidage below:
Number/tested area (individual/the cm of porosity=spot
2)
When calculating number of apertures, do following calculating by spot diameter size: hot spot diameter is less than 1mm, and with a porosimeter at often; Be greater than 1mm and be less than 3mm often o'clock with three porosimeters; Be greater than 3mm and be less than 5mm, often with ten porosimeters.
The test result of the coating of embodiment 1 ~ 6 and comparative example and the performance of plating solution is as follows:
As can be seen from the above table, in embodiment 1 ~ 6, consider from the integration test effect of plating solution and coating, the dispersive ability of the formula plating solution of embodiment 6, depth capability, Surface flat, current efficiency and plating speed, the porosity of coating and bonding force will be got well compared with other embodiment.Thus, this formula is screening formulation of the present invention, and the preferred plating conditions of its correspondence is the pulsewidth of monopulse rectangular wave current is 3ms, and dutycycle is 10%, and average current density is 2.5A/dm
2; PH is 12.5, and temperature is 50 DEG C, and electroplating time is 50min.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. an electroplate liquid for edta salt cyanide-free copper electroplating, is characterized in that, comprises the Cu that content is 15 ~ 25g/L
2(OH)
2cO
3, content is the edta salt of 120 ~ 160g/L, content is 20 ~ 40g/L Diethylenetriaminee (DETA) and content is the nitrate of 2 ~ 8g/L.
2. electroplate liquid according to claim 1, is characterized in that, described edta salt is EDETATE SODIUM and/or four sodium.
3. electroplate liquid according to claim 1, is characterized in that, comprises the Cu that content is 22g/L
2(OH)
2cO
3, content is the EDETATE SODIUM of 150g/L, content is 32g/L Diethylenetriaminee (DETA) and content is the nitrate of 4g/L.
4. electroplate liquid according to claim 1, is characterized in that, described nitrate is ammonium nitrate.
5. use the electroplate liquid electric plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 15 ~ 25g Cu
2(OH)
2cO
3, 120 ~ 160g edta salt, 20 ~ 40g Diethylenetriaminee (DETA) and 2 ~ 8g nitrate;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
6. method according to claim 5, is characterized in that, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 1 ~ 3ms, and dutycycle is 5 ~ 30%, and average current density is 1 ~ 3A/dm
2.
7. method according to claim 5, is characterized in that, in described step (2), the pH of electroplate liquid is 11 ~ 13.
8. method according to claim 5, is characterized in that, the temperature of electroplate liquid is 40 ~ 60 DEG C.
9. method according to claim 5, is characterized in that, the time of plating is 40 ~ 60min.
10. method according to claim 5, is characterized in that, in described step (2), the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 1.
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|---|---|---|---|
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|---|---|---|---|
| CN201310557212.5A CN104630846A (en) | 2013-11-08 | 2013-11-08 | Electroplating solution for EDTA salt cyanide-free copper plating and electroplating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825861A (en) * | 2019-03-18 | 2019-05-31 | 辽宁科技大学 | A pure iron-based alkaline electroplating copper coating process |
| CN114657611A (en) * | 2022-04-20 | 2022-06-24 | 佛山市诺诚科技有限公司 | Alkaline copper electroplating solution and electroplating method thereof |
-
2013
- 2013-11-08 CN CN201310557212.5A patent/CN104630846A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825861A (en) * | 2019-03-18 | 2019-05-31 | 辽宁科技大学 | A pure iron-based alkaline electroplating copper coating process |
| CN114657611A (en) * | 2022-04-20 | 2022-06-24 | 佛山市诺诚科技有限公司 | Alkaline copper electroplating solution and electroplating method thereof |
| CN114657611B (en) * | 2022-04-20 | 2024-03-12 | 佛山市诺诚科技有限公司 | Alkaline copper electroplating solution and electroplating method thereof |
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