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 PDF

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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
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cadmium
plating
acid
component
complexant
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CN106245071B (en
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郭崇武
赖奂汶
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Guangzhou Ultra Union Chemicals Ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/26Electroplating: Baths therefor from solutions of cadmium

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

Acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology
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.
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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
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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

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