CN106245071A - Acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology - Google Patents
Acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology Download PDFInfo
- Publication number
- CN106245071A CN106245071A CN201610785483.XA CN201610785483A CN106245071A CN 106245071 A CN106245071 A CN 106245071A CN 201610785483 A CN201610785483 A CN 201610785483A CN 106245071 A CN106245071 A CN 106245071A
- Authority
- CN
- China
- Prior art keywords
- cadmium
- plating
- acid
- component
- complexant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 107
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 69
- 239000002253 acid Substances 0.000 title claims abstract description 31
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000009713 electroplating Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000654 additive Substances 0.000 title claims abstract description 11
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract 18
- 238000005516 engineering process Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 35
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 239000002671 adjuvant Substances 0.000 claims abstract description 20
- 239000001103 potassium chloride Substances 0.000 claims abstract description 11
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 230000008901 benefit Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 propoxyl group Chemical group 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 6
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000306 component Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 3
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 3
- 235000012141 vanillin Nutrition 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- JZJXKEWVUBVOEH-UHFFFAOYSA-N n,n-diethylprop-2-yn-1-amine Chemical compound CCN(CC)CC#C JZJXKEWVUBVOEH-UHFFFAOYSA-N 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- PBHRBFFOJOXGPU-UHFFFAOYSA-N cadmium Chemical compound [Cd].[Cd] PBHRBFFOJOXGPU-UHFFFAOYSA-N 0.000 description 52
- 239000011651 chromium Substances 0.000 description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- NHMJUOSYSOOPDM-UHFFFAOYSA-N cadmium cyanide Chemical compound [Cd+2].N#[C-].N#[C-] NHMJUOSYSOOPDM-UHFFFAOYSA-N 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- PKOUHMSMLLYQOS-UHFFFAOYSA-N [Cd].N(CCO)(CCO)CCO Chemical compound [Cd].N(CCO)(CCO)CCO PKOUHMSMLLYQOS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- YUNONZJRSYCEGP-UHFFFAOYSA-N cadmium oxalonitrile Chemical compound N#CC#N.[Cd] YUNONZJRSYCEGP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C25D3/26—Electroplating: Baths therefor from solutions of cadmium
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 acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology, each component of plating solution is as follows: Caddy (Cleary) 35～40g/L, potassium chloride 140～180g/L, complexant 120～160g/L, brightener 1.5～2.5mL/L, adjuvant 25～35mL/L；Electroplating manipulation condition is: coating bath temperature 15～35 DEG C, cathode-current density 0.5～1.5A/dm2, negative electrode is 2:1 with the ratio of annode area, and anode has cadmium plate and plating high-density graphite plate bi-material.Advantages of the present invention mainly has: by using high-performance electroplating additive intermediate preparation brightener and adjuvant, uses combination complexant to generate polynary complex ion with cadmium ion, improves plating solution performance and coating performance；This technique bath stability, it is easy to safeguard, current efficiency is higher, covering power is strong, coating fragility is little, corrosion resisting property is good, and properties meets the requirement of aerospace industry ministerial standard QJ 453 1988 " cadmium plating layer technical conditions ", and electroplating wastewater processing result meets the requirement of GB 21,900 2008 " plating pollutant emission standard " table 3.
Description
Technical field
The present invention relates to field of electroplating, particularly relate to acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology.
Background technology
Cadmium plating layer has corrosion resistance and the flexibility of excellence, is once widely used.Cadmium and compound thereof have
Certain toxicity, in 20 end of the centurys, cadmium plating technique has been eliminated in product for civilian use plating the most substantially, but due to Aero-Space, navigation and
The particularity requirement of some electronic products, some enterprises also retain a certain amount of cadmium plating technique at present.Traditional cyanide cadmium is molten
Liquid and constant product quality, but cyanide is country forbids strictly one of pollutant of using, replaces cyaniding plating with non-cyanide plating cadmium
Cadmium is the most imperative, and it is pressed for time.China carried out some researchs to non-cyanide plating cadmium, but relatively fewer.Alkaline non-cyanide
Cadmium plating includes making the cadmium plating technique of complexant with triethanolamine and nitrilotriacetic acid and making the cadmium plating technique of complexant with HEDP[1-2]。
There is the problem of bath stability difference in triethanolamine cadmium plating, HEDP cadmium plating exists that current efficiency is low and waste water difficult treatment etc. is asked
Topic, therefore both technique yet there are no the production application of scale.Acid non-cyanide plating cadmium technique has put into industrialized production[3-6],
But plating solution needs add ethylenediaminetetraacetic acid and ammonium chloride, bring the biggest difficulty to electroplating wastewater processing[7]So that it is application is subject to
Arrive restriction.
According to the requirement of National Development and Reform Commission's " industry restructuring catalogue (revision in 2011) ", National Guizhou Aviation
Aerospace enterprise group carries out eliminating the work of cyanide cadmium technique, uses the acid non-cyanide plating cadmium technique containing EDTA at present, but plates
After layer olive passivation, phenomenon of growing dim occurs, and electroplating wastewater cadmium exceeds standard.At the invitation of Guiyang Surface Engineering employer's organization,
Guangzhou Chao Bang Chemical Co., Ltd. has carried out the developmental research of non-cyanide plating cadmium technique.
Wherein list of references:
[1] Wu Chang, Xue Yongfei, Lu Yamei, etc. the discussion [J] of alkaline non-cyanide cadmium plating technique. material protection, 1974,15
(6): 1-9；
[2] Zhang Yuncheng, Hu Runan, Xiang Rong. plating handbook [M]. Beijing: National Defense Industry Press, 1997:279；
[3] Yang Fengxuan. the non-cyanide plating with DPE-Ш as additive is every [J]. corrosion packaging, 1983,12 (4): 5-8；
[4] Yang Qinjian. non-cyanide plating cadmium is in the application [J] of our factory. plating and environmental protection, 1996,16 (2): 29-30；
[5] Huangping, Chen Duanjie. non-cyanide plating cadmium technical study and application [J]. New Technologies, 2008,30 (11): 17-
18；
[6] Wan Binghua, Yang Jun, Wang Fuxin, etc. the research of non-cyanide plating cadmium process exploitation and application [J]. plating and finish,
2014,36 (3): 22-25+46；
[7] Yang Qianfang, Feng Shuying, Liu Fang. non-cyanide plating cadmium waste water treatment research [J]. Sichuan environment, 1982,4 (1): 36-
39。
Summary of the invention
The purpose of the present invention is to propose to acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology, to solve current nothing
Cyanogen cadmium plating plating solution and the problem such as quality of coating is poor and electroplating wastewater processing is difficult.
The technical scheme is that and be achieved in that:
Acid non-cyanide plating cadmium additive, including following component: complexant, brightener, adjuvant.
Described complexant includes tri-kinds of components of A, B, C, and wherein component A includes that nitrilotriacetic acid, B component include citric acid, wine
Any one or two kinds in stone acid, gluconic acid, malic acid, component C include malonic acid, butadiene dilute acid, the dilute diacid of anti-fourth,
Tri-kinds of component mix homogeneously of described A, B, C are obtained described complexant by any one or two kinds in oxalic acid.
More preferably, described complexant is added in container in following ratio and is uniformly mixed: A, 300～400g, B, 300～
500g, C, 200～400g.
Described brightener includes tri-kinds of components of D, E, F, and wherein D component includes α-vinyl-N-propane sulfonic acid yl pyridines inner salt
(CAS NO.6613-64-5), component E includes Vanillin, Veratraldehyde, 4-methoxyl group
Any one or two kinds in benzaldehyde, F component includes propilolic alcohol ethyoxyl ether, propilolic alcohol propoxyl group ether, N, N-diethyl third
Ynamine, N, N-PABS, N, any one or two kinds in N-diethyl propargylamine sulfate, by D, E, F
Three kinds of components are dissolved in isopropanol and water mixed solution and obtain described brightener.
More preferably, described brightener is prepared in following ratio and method: add the mixing of 300mL isopropanol in 400mL water all
Even, add D component 30～80g, component E 30～50g, F component 60～100g, stirring is completely dissolved to component E, and benefit adds water to
1000mL。
Described adjuvant includes water-soluble polyacrylamide, 2-ethylhexylsulfate sodium salt, N, N, N-tri-(2-hydroxypropyl
Base)-N'-hydroxyethylethylene diamine, G component and a kind of condensation substance being made up of with epoxychloropropane ethylenediamine, dimethyl propylamine,
Described G component is consistent with the F component in described brightener.
More preferably, described adjuvant is prepared in following ratio and method: 50～80g IC 113 water-soluble polypropylene acyls
Amine, 20～50g ethylenediamine and dimethyl propylamine and epichlorohydrin condensate, 30～80g 2-ethylhexylsulfate sodium salt,
10～30g N, N, N-tri-(2-hydroxypropyl)-N'-hydroxyethylethylene diamine and 30～60g G components add in 700g water, stirring
Make it dissolve, then benefit adds water to 1000mL.Described IC 113 water-soluble polyacrylamide is by Bluclad S.R.L. supplier
There is provided.
The preparation method of acid non-cyanide plating cadmium solution, step is as follows:
A () is pressed plating solution volume and is calculated the water adding 4/5 in coating bath, be sequentially added into sodium hydroxide, potassium chloride, complexant,
Sodium hydroxide is 1:2 with the mass ratio of complexant, and stirring makes above-mentioned substance dissolve；
B () is subsequently adding Caddy (Cleary), and stir to dissolving, and filters plating solution；
C () is sequentially added into brightener, adjuvant, with dilute hydrochloric acid or the regulation plating of sodium hydroxide solution that mass fraction is 10%
Between the pH of liquid to 6.0～7.0, add water to the volume of regulation, at 0.1A/dm21～8h it is electrolysed under electric current density；
In last plating solution, potassium chloride concentration reaches 140～180g/L, and complexant concentration reaches 120～160g/L, Caddy (Cleary)
Concentration reaches 32～40g/L, and brightener concentration reaches 1.5～2.5mL/L, and adjuvant concentration reaches 25～35mL/L.
Acid non-cyanide plating cadmium technique, step is as follows:
(1) unplated piece pre-treatment；
(2) the acid non-cyanide plating cadmium solution of preparation；
(3) electroplating, during plating, coating bath temperature is 15～35 DEG C, and cathode-current density is 0.5～1.5A/dm2。
Further, negative electrode is 2:1 with the ratio of annode area, and anode is cadmium plate and the plating use of cadmium content >=99.97%
High-density graphite plate, described cadmium plate is 1:1～1:2 with the area ratio of graphite cake.
The invention have the benefit that and use function admirable and the less intermediate preparation brightener and auxiliary of adsorptivity
Agent, reduces the inclusion content of coating, improves flexibility and the corrosion resistance of coating, uses combination complexant to generate polynary with cadmium ion
Complex ion, makes cadmium ion reach preferably sedimentation potential, improves covering power and the covering power of plating solution, uses coordination ability to fit
In complexing agent cadmium ion, reduce cadmium plating waste water process difficulty, make described plating solution and coating performance meet space flight work
The requirement of industry ministerial standard QJ 453-1988 " cadmium plating layer technical conditions ", cadmium plating waste water result meets GB 21900-2008
The requirement of " plating pollutant emission standard " table 3.
Detailed description of the invention
For being more fully understood that the present invention, below by following example the present invention made the most concrete elaboration, but not
Can be regarded as limitation of the invention, some made according to foregoing invention content for those skilled in the art are nonessential
Improve and adjust, be also considered as being within the scope of the present invention.
Embodiment 1:
The acidity of the present embodiment is as follows without cyanogen rack plating cadmium solution composition and concentration:
Caddy (Cleary) 37g/L, potassium chloride 160g/L, complexant 140g/L, brightener 2mL/L, adjuvant 30mL/L；
Operating condition during plating is as follows:
Coating bath temperature is 15～35 DEG C, and cathode-current density is 0.5～1.5A/dm2, negative electrode is 2 with the ratio of annode area:
1, anode is cadmium plate and the plating high-density graphite plate of cadmium content >=99.97%, described cadmium plate and the area ratio of graphite cake
For 1:1～1:2.
Described complexant is made up of tri-kinds of components of A, B, C, and wherein component A is nitrilotriacetic acid, and B component is by citric acid, winestone
Any one or two kinds of compositions in acid, gluconic acid, malic acid, component C by malonic acid, butadiene dilute acid, the dilute diacid of anti-fourth,
Any one or two kinds of compositions in oxalic acid, complexant presses following proportions: A, 300～400g；B, 300～500g；C、200
～400g, all add in container and be uniformly mixed.
Described brightener is made up of tri-kinds of components of D, E, F, and wherein D component is α-vinyl-N-propane sulfonic acid yl pyridines inner salt
(CAS NO.6613-64-5), component E is by Vanillin, Veratraldehyde, 4-methoxybenzene
Any one or two kinds of compositions in formaldehyde, F component is by propilolic alcohol ethyoxyl ether, propilolic alcohol propoxyl group ether, N, N-diethyl third
Ynamine, N, N-PABS, N, any one or two kinds of one-tenth in N-diethyl propargylamine sulfate are grouped into.
Brightener is prepared in following ratio and method: add 300mL isopropanol mix homogeneously in 400mL water, by tri-kinds of components of D, E and F
It is dissolved in isopropanol and water mixed liquid by 30～80g, 30～50g and 60～100g respectively, adds water to 1000mL.
Described adjuvant is prepared by following method: 50～80g IC 113 water-soluble polyacrylamides, 20～50g are by second
Condensation substance, 30～80g 2-ethylhexylsulfate sodium salt, 10～the 30g that diamidogen, dimethyl propylamine form with epoxychloropropane
N, N, N-tri-(2-hydroxypropyl)-N'-hydroxyethylethylene diamine and 30～60g G components (G component and the F component one in brightener
Cause) add in 700g water, stirring makes it dissolve, then benefit adds water to 1000mL.
Described acid non-cyanide plating cadmium solution is prepared by following method:
A () is pressed plating solution volume and is calculated the water adding 4/5 in coating bath, be sequentially added into sodium hydroxide, potassium chloride, complexant,
Sodium hydroxide is 1:2 with the mass ratio of complexant, and stirring makes above-mentioned substance dissolve；
B () is subsequently adding Caddy (Cleary), and stir to dissolving, and filters plating solution；
C () is sequentially added into brightener, adjuvant, with dilute hydrochloric acid or the regulation plating of sodium hydroxide solution that mass fraction is 10%
The pH of liquid to 6.5, adds water to the volume of regulation, at 0.1A/dm21～8h it is electrolysed under electric current density；
In last plating solution, potassium chloride concentration reaches 160g/L, and complexant concentration reaches 140g/L, and Caddy (Cleary) concentration reaches
37g/L, brightener concentration reaches 2mL/L, and adjuvant concentration reaches 30mL/L.
Described acidity is as follows without the plating solution of cyanogen rack plating cadmium technique and coating performance and cadmium plating waste water result:
Deposition velocity: at Jk=1A/dm2Lower plating, v=0.33 μm/min；
Current efficiency: at Jk=1A/dm2Lower plating, current efficiency is 73%；
Covering power: 41%～52%.
Covering power: with the iron pipe plating that internal diameter is 10mm, with 1.0A/dm2Electric current density plating 30min, Cr VI is low
After chromium chromatic passivation, coating length is 9.2 with the ratio in aperture；
Coating corrosion resistance: take steel and iron parts by this technique cadmium plating 30min, use Cr VI low chromium colorful passivating process blunt
Change, aging 15min at 60 DEG C, then place more than 24h.According to GB/T 10,125 1997, " artificial atmosphere corrosion testing salt fog tries
Test " carry out neutral salt spray test 2000h, cadmium plating layer generates without white rust, than aerospace industry ministerial standard QJ 453-1988 " cadmium plating layer
Technical conditions " requirement of 96h neutral salt spray test is high more than 20 times.
Cadmium plating waste water processes: described cadmium plating waste water SDD precipitates cadmium ion, cadmium after process
The mass concentration of ion is 0.005mg/L, meets the requirement of GB 21900-2008 " plating pollutant emission standard " table 3.
Embodiment 2:
The acidity of the present embodiment is as follows without cyanogen barrel plating cadmium solution composition and concentration:
Caddy (Cleary) 34g/L, potassium chloride 180g/L, complexant 150g/L, brightener 2mL/L, adjuvant 30mL/L；
Operating condition during plating is as follows:
Coating bath temperature is 15～35 DEG C, and coating bath voltage is 4～7V, and drum rotating speed is 3～5r/min, negative electrode and annode area
Ratio be 2:1, anode is the cadmium plate+plating high-density graphite plate of cadmium content >=99.97%, the face of described cadmium plate and graphite cake
Long-pending ratio is 1:1～1:2.
Described complexant, brightener and adjuvant preparation method are such as embodiment 1.
Described acid non-cyanide plating cadmium solution is prepared by following method:
A () is pressed plating solution volume and is calculated the water adding 4/5 in coating bath, be sequentially added into sodium hydroxide, potassium chloride, complexant,
Sodium hydroxide is 1:2 with the mass ratio of complexant, and stirring makes above-mentioned substance dissolve；
B () is subsequently adding Caddy (Cleary), and stir to dissolving, and filters plating solution；
C () is sequentially added into brightener, adjuvant, with dilute hydrochloric acid or the regulation plating of sodium hydroxide solution that mass fraction is 10%
The pH of liquid to 6.5, adds water to the volume of regulation, at 0.1A/dm21～8h it is electrolysed under electric current density；
In last plating solution, potassium chloride concentration reaches 180g/L, and complexant concentration reaches 150g/L, and Caddy (Cleary) concentration reaches
34g/L, brightener concentration reaches 2mL/L, and adjuvant concentration reaches 30mL/L.
Described acidity is as follows without the plating solution of cyanogen barrel plating cadmium technique and coating performance and cadmium plating waste water result:
Deposition velocity: at Jk=1A/dm2Lower plating, v=0.29 μm/min；
Current efficiency: at Jk=1A/dm2Lower plating, current efficiency is 68%；
Covering power: 48%～67%；
Covering power: with the iron pipe plating that internal diameter is 10mm, with 1.0A/dm2Electric current density plating 30min, Cr VI is low
After chromium chromatic passivation, coating length is 9.4 with the ratio in aperture.
Coating corrosion resistance: take steel and iron parts by this technique cadmium plating 30min, use Cr VI low chromium colorful passivating process blunt
Change, aging 15min at 60 DEG C, then place more than 24h.According to GB/T 10,125 1997, " artificial atmosphere corrosion testing salt fog tries
Test " carry out neutral salt spray test 2000h, cadmium plating layer generates without white rust, than aerospace industry ministerial standard QJ 453-1988 " cadmium plating layer
Technical conditions " requirement of 96h neutral salt spray test is high more than 20 times.
Cadmium plating waste water processes: described cadmium plating waste water SDD precipitates cadmium ion, cadmium after process
The mass concentration of ion is 0.007mg/L, meets the requirement of GB 21900-2008 " plating pollutant emission standard " table 3.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (9)
1. acid non-cyanide plating cadmium additive, it is characterised in that include following component: complexant, brightener, adjuvant；
Described complexant includes tri-kinds of components of A, B, C, wherein component A include nitrilotriacetic acid, B component include citric acid, tartaric acid,
Any one or two kinds in gluconic acid, malic acid, component C includes malonic acid, butadiene dilute acid, the dilute diacid of anti-fourth, oxalic acid
In any one or two kinds, tri-kinds of component mix homogeneously of described A, B, C are obtained described complexant；
Described brightener includes tri-kinds of components of D, E, F, and wherein D component includes α-vinyl-N-propane sulfonic acid yl pyridines inner salt (CAS
NO.6613-64-5), component E includes Vanillin, Veratraldehyde, 4-methoxybenzene first
Any one or two kinds in aldehyde, F component include propilolic alcohol ethyoxyl ether, propilolic alcohol propoxyl group ether, N, N-diethyl propargylamine,
N, N-PABS, N, any one or two kinds in N-diethyl propargylamine sulfate, by tri-kinds of groups of D, E, F
Divide to be dissolved in isopropanol and water mixed solution and obtain described brightener；
Described adjuvant includes water-soluble polyacrylamide, 2-ethylhexylsulfate sodium salt, N, N, N-tri-(2-hydroxypropyl)-
N'-hydroxyethylethylene diamine, G component and the condensation substance being made up of with epoxychloropropane ethylenediamine, dimethyl propylamine, described G group
Divide consistent with the F component in described brightener.
2. acid non-cyanide plating cadmium additive as claimed in claim 1, it is characterised in that: described complexant is added in following ratio
Container is uniformly mixed: A, 300～400g, B, 300～500g, C, 200～400g.
3. acid non-cyanide plating cadmium additive as claimed in claim 1, it is characterised in that: described brightener is in following ratio and side
Prepared by method: add 300mL isopropanol mix homogeneously in 400mL water, add D component 30～80g, component E 30～50g, F component 60
～100g, stir and be completely dissolved to component E, mend and add water to 1000mL.
4. non-cyanide plating cadmium additive as claimed in claim 1 acid, it is characterised in that: described adjuvant by following ratio with
Prepared by method: 50～80g water-soluble polyacrylamides, 20～50g ethylenediamine and dimethyl propylamine and epichlorohydrin condensate,
30～80g 2-ethylhexylsulfate sodium salts, 10～30g N, N, N-tri-(2-hydroxypropyl)-N'-hydroxyethylethylene diamine and 30
～60g G component adds in 700g water, stirring makes it dissolve, then benefit adds water to 1000mL.
5. the preparation method of acid non-cyanide plating cadmium solution, it is characterised in that: prepared by following method:
A () is pressed plating solution volume and is calculated the water adding 4/5 in coating bath, add sodium hydroxide, potassium chloride, complexant, sodium hydroxide
Being 1:2 with the mass ratio of complexant, stirring makes above-mentioned substance dissolve；
B () is subsequently adding Caddy (Cleary), and stir to dissolving, and filters plating solution；
C () adds brightener, adjuvant, with dilute hydrochloric acid or the pH value of sodium hydroxide solution that mass fraction is 10% regulation plating solution
To between 6.0～7.0, add water to the volume of regulation, at 0.1A/dm21～8h it is electrolysed under electric current density；
In the plating solution finally obtained, potassium chloride concentration reaches 140～180g/L, and complexant concentration reaches 120～160g/L, chlorination
Cadmium concentration reaches 32～40g/L, and brightener concentration reaches 1.5～2.5mL/L, and adjuvant concentration reaches 25～35mL/L.
6. acid non-cyanide plating cadmium technique, it is characterised in that:
(1) unplated piece pre-treatment；
(2) the acid non-cyanide plating cadmium solution of preparation；
(3) electroplating, during plating, coating bath temperature is 15～35 DEG C, and cathode-current density is 0.5～1.5A/dm2。
7. the most acid non-cyanide plating cadmium technique, it is characterised in that:
Negative electrode is 2:1 with the ratio of annode area.
8. the most acid non-cyanide plating cadmium technique, it is characterised in that:
Described anode is cadmium plate and the plating graphite cake of cadmium content >=99.97%.
9. the most acid non-cyanide plating cadmium technique, it is characterised in that:
Described cadmium plate is 1:1～1:2 with the area ratio of graphite cake.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610785483.XA CN106245071B (en) | 2016-08-31 | 2016-08-31 | Acid non-cyanide plating cadmium additive, plating solution prepares and electroplating technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610785483.XA CN106245071B (en) | 2016-08-31 | 2016-08-31 | Acid non-cyanide plating cadmium additive, plating solution prepares and electroplating technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106245071A true CN106245071A (en) | 2016-12-21 |
| CN106245071B CN106245071B (en) | 2018-06-29 |
Family
ID=58080469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610785483.XA Active CN106245071B (en) | 2016-08-31 | 2016-08-31 | Acid non-cyanide plating cadmium additive, plating solution prepares and electroplating technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106245071B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400907A (en) * | 2017-08-24 | 2017-11-28 | 重庆立道表面技术有限公司 | Alkaline non-cyanide cadmium plating removes hydrogen embrittlement agent and its electroplate liquid, the preparation method of electroplate liquid |
| CN108385138A (en) * | 2018-03-19 | 2018-08-10 | 广州超邦化工有限公司 | A kind of preparation method for the metal surface coating structure being applicable under Yu Haiyang strong corrosive environment |
| CN109097799A (en) * | 2018-09-19 | 2018-12-28 | 重庆立道新材料科技有限公司 | A kind of alkaline non-cyanide cadmium plating cleaner and its application |
| CN109594106A (en) * | 2019-02-15 | 2019-04-09 | 广州超邦化工有限公司 | The method for removing of potassium chloride non-cyanide plating cadmium failure as caused by tin impurity |
| CN110117782A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | A kind of non-cyanide plating cadmium titanium alloy and trivalent chromium passivation coating and preparation method thereof |
| CN110117803A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology |
| CN110172685A (en) * | 2019-05-23 | 2019-08-27 | 南京宁甬天星汽车电器有限公司 | Magnetic switch metal conditioner and magnetic switch process of surface treatment |
| CN110205629A (en) * | 2019-06-18 | 2019-09-06 | 广州超邦化工有限公司 | A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process |
| CN112359402A (en) * | 2020-10-20 | 2021-02-12 | 上海航翼高新技术发展研究院有限公司 | Automatic cyanide-free cadmium plating device system and process for aviation parts |
| CN113755910A (en) * | 2021-09-18 | 2021-12-07 | 中国航发北京航空材料研究院 | A kind of cyanide-free cadmium electroplating solution with alkyl glycoside as additive component |
| CN114197002A (en) * | 2021-12-13 | 2022-03-18 | 中国航发南方工业有限公司 | Cyanide cadmium plating barrel plating method for aircraft engine parts |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4855136A (en) * | 1971-11-15 | 1973-08-02 | ||
| RU2302483C1 (en) * | 2006-03-13 | 2007-07-10 | Открытое акционерное общество Научно-производственное объединение "Искра" | Cadmium-plating electrolyte |
| CN101942681A (en) * | 2010-06-28 | 2011-01-12 | 重庆长安工业(集团)有限责任公司 | Process for plating cadmium on shaped steel part with deep/blind hole |
| CN105441992A (en) * | 2015-11-26 | 2016-03-30 | 贵阳华科电镀有限公司 | Ammonium chloride cadmium plating electroplating process and electroplating liquid |
| CN105648482A (en) * | 2016-03-25 | 2016-06-08 | 贵州航天精工制造有限公司 | Cyanide-free cadmium plating process for part surface |
-
2016
- 2016-08-31 CN CN201610785483.XA patent/CN106245071B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4855136A (en) * | 1971-11-15 | 1973-08-02 | ||
| RU2302483C1 (en) * | 2006-03-13 | 2007-07-10 | Открытое акционерное общество Научно-производственное объединение "Искра" | Cadmium-plating electrolyte |
| CN101942681A (en) * | 2010-06-28 | 2011-01-12 | 重庆长安工业(集团)有限责任公司 | Process for plating cadmium on shaped steel part with deep/blind hole |
| CN105441992A (en) * | 2015-11-26 | 2016-03-30 | 贵阳华科电镀有限公司 | Ammonium chloride cadmium plating electroplating process and electroplating liquid |
| CN105648482A (en) * | 2016-03-25 | 2016-06-08 | 贵州航天精工制造有限公司 | Cyanide-free cadmium plating process for part surface |
Non-Patent Citations (2)
| Title |
|---|
| 郭崇武 等: "新型酸性无氰镀镉工艺的开发研究", 《第十一届全国转化膜及表面精饰学术年会论文集》 * |
| 郭崇武: "新型酸性无氰镀镉工艺的开发研究", 《电镀与涂饰》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400907A (en) * | 2017-08-24 | 2017-11-28 | 重庆立道表面技术有限公司 | Alkaline non-cyanide cadmium plating removes hydrogen embrittlement agent and its electroplate liquid, the preparation method of electroplate liquid |
| CN108385138A (en) * | 2018-03-19 | 2018-08-10 | 广州超邦化工有限公司 | A kind of preparation method for the metal surface coating structure being applicable under Yu Haiyang strong corrosive environment |
| CN109097799A (en) * | 2018-09-19 | 2018-12-28 | 重庆立道新材料科技有限公司 | A kind of alkaline non-cyanide cadmium plating cleaner and its application |
| CN109594106A (en) * | 2019-02-15 | 2019-04-09 | 广州超邦化工有限公司 | The method for removing of potassium chloride non-cyanide plating cadmium failure as caused by tin impurity |
| CN110117782A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | A kind of non-cyanide plating cadmium titanium alloy and trivalent chromium passivation coating and preparation method thereof |
| CN110117803A (en) * | 2019-05-14 | 2019-08-13 | 广州超邦化工有限公司 | Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology |
| CN110172685A (en) * | 2019-05-23 | 2019-08-27 | 南京宁甬天星汽车电器有限公司 | Magnetic switch metal conditioner and magnetic switch process of surface treatment |
| CN110205629A (en) * | 2019-06-18 | 2019-09-06 | 广州超邦化工有限公司 | A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process |
| CN112359402A (en) * | 2020-10-20 | 2021-02-12 | 上海航翼高新技术发展研究院有限公司 | Automatic cyanide-free cadmium plating device system and process for aviation parts |
| CN113755910A (en) * | 2021-09-18 | 2021-12-07 | 中国航发北京航空材料研究院 | A kind of cyanide-free cadmium electroplating solution with alkyl glycoside as additive component |
| CN114197002A (en) * | 2021-12-13 | 2022-03-18 | 中国航发南方工业有限公司 | Cyanide cadmium plating barrel plating method for aircraft engine parts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106245071B (en) | 2018-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106245071B (en) | Acid non-cyanide plating cadmium additive, plating solution prepares and electroplating technology | |
| CN101736337B (en) | Method for preparing chromium-free passivation solution, and method for passivating electrogalvanizing or zinc alloy layer by using same | |
| CN101876071B (en) | Environmentally-friendly black chrome-silver-free zinc-plating passivation solution and preparation method thereof | |
| CN104328395B (en) | Phosphorus chemistry nickel plating concentrated solution and plating technology in one | |
| CN107740085B (en) | A kind of environment-friendly composite color passivation solution and preparation method thereof | |
| CN105779988A (en) | Chromate-free passivation solution for electroplated zinc and passivation technology thereof | |
| CN109518237B (en) | Zinc-nickel-phosphorus electroplating solution, preparation method thereof and electroplating method | |
| CN106435550A (en) | Phosphorizing liquid, reinforcement surface normal-temperature phosphorizing film and preparation method thereof | |
| CN102995077A (en) | Cyanide-free alkaline bright copper plating solution and preparation method and electroplating process thereof | |
| CN111455419B (en) | Metal surface zinc-nickel alloy electroplating solution and electroplating process | |
| CN102953055A (en) | Black phosphating liquid and use method thereof | |
| CN104073796A (en) | Metal plating passivation solution and preparation method thereof | |
| CN104805480A (en) | Alkaline zinc-nickel electroplating liquid, preparation method and electroplating method | |
| CN104962893A (en) | Environmental phosphating solution | |
| CN103014788A (en) | Cyanide-free alkaline copper-plating brightener and preparation method for same | |
| CN102560568A (en) | Additive for chloride zincification and preparation method and application thereof | |
| CN104451634B (en) | Aluminum and aluminum alloy passivation solution, preparation method and using method thereof | |
| CN105734622A (en) | Cyanide-free copper plating solution and preparation method thereof | |
| CN107574430A (en) | A kind of silicate bright blue passivation liquid and preparation method thereof | |
| CN106756939A (en) | aluminum passivation liquid and preparation method thereof | |
| CN108754468A (en) | Galvanizing chrome-free tanning agent | |
| CN102140631B (en) | Environment-friendly high-phosphorus chemical nickel additive | |
| CN104911645A (en) | Alkaline cyanide-free zinc plating agent and application method thereof | |
| CN103540921B (en) | A kind of electrogalvanizing environmental protection passivating solution | |
| CN101654783B (en) | Method for preparing silicate colorized passivating liquid for galvanization member |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 510000 Guangzhou, Guangdong Province, Baiyun District, Jianggao Town, Shen Shan Guo Tang Guo Ya Road 88 Patentee after: Guangzhou Chao Bang Chemical Co., Ltd. Address before: 510000 Shaoguan, Guangdong Province, Baiyun District, Jianggao Town, Shen Shan Guo Tang Guo Ya Road 88 Patentee before: Guangzhou Chao Bang Chemical Co., Ltd. |