CN110117803A - Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology - Google Patents
Potassium chloride is without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology Download PDFInfo
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- CN110117803A CN110117803A CN201910399359.3A CN201910399359A CN110117803A CN 110117803 A CN110117803 A CN 110117803A CN 201910399359 A CN201910399359 A CN 201910399359A CN 110117803 A CN110117803 A CN 110117803A
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- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- 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
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- 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
- C25D5/48—After-treatment of electroplated surfaces
Abstract
The invention discloses potassium chloride without cyanogen cadmium titanium alloy plating solution, preparation method and electroplating technology, plating solution each component is as follows: 20~35g/L of caddy, 80~140g/L of complexant, 120~200g/L of potassium chloride, 1~5g/L of sodium fluoride, titanium salt feed 2~5mL/L of agent, 1~3mL/L of brightener, 20~40mL/L of adjuvant, walk 5~15mL/L of agent；Electroplating manipulation condition are as follows: bath pH value 6.5~7.5,20~35 DEG C of coating bath temperature, 0.5~2A/dm of cathode-current density2, the ratio between cathode and annode area are 2 ︰ (1~3).Bath stability of the present invention, convenient for safeguarding, technique hydrogen brittleness is small, and cadmium titanium alloy coating has excellent corrosion resistance, has preferable market prospects.
Description
Technical field
The present invention relates to field of electroplating, in particular to potassium chloride is without cyanogen cadmium titanium alloy electroplating technology.
Background technique
With the development of high-altitude high-speed aircraft, aircraft industry largely uses high-strength structure material, but this kind of material
Deadly defect is that Hydrogen Embrittlement is big, has the tendency that stress corrosion cracking.Therefore, avoiding hydrogen embrittlement is the processing of high-strength structure material
The problem of with that must be given one's full attention in use process.To prevent the hydrogen embrittlement in electroplating process, it is desirable that in 200 DEG C of conditions after plating
The lower baking dehydrogenation for carrying out 20h or more, and use porosity plating to improve dehydrogenation effect, but the protective performance of porosity electroplated layer is very
Difference is not able to satisfy requirement.The beginning of the sixties in last century, Japanese Koji Ta-kata et al. have invented cyanide cadmium titanium alloy work
Skill, it was demonstrated that the cadmium titanium alloy coating of titaniferous 0.1%~0.7% has excellent corrosion stability and low hydrogen brittleness, can be used as high intensity
The protective layer of structural steel.The U.S. has introduced this technique, and is used as the protective layer of certain aircraft high strength steel structural members.But because of this
Kind electroplate liquid is to be added in the alkaline cyanide cadmium solution without brightener to form after dissolving pertitanate with hydrogen peroxide, and titanium salt exists
Extremely unstable in plating solution, precipitating susceptible to hydrolysis, so needing circulating filtration, operation and technology controlling and process are all very complicated.With environmental protection
The continuous improvement of consciousness, limitation or the use of superseded cyanide electroplating technology are being give stricted orders by national governments at this stage.
Domestic-developed in 1970 is without cyanogen cadmium titanium alloy electroplate liquid, with dissolving with hydrochloric acid TiOCi2After be added to ammonium salt non-cyanide plating cadmium
In solution, using the cadmium titanium alloy coating of the available titaniferous 0.1%~0.7% of this electroplate liquid.This ammonium salt non-cyanide plating cadmium
Titanium alloy solution makees complexant using EDTA and nitrilotriacetic acid, and very big difficulty is brought to electroplating wastewater processing.This plating solution
Brightener is made using thiocarbamide and gum arabic, thiocarbamide is mingled with more in coating, declines corrosion resistance of coating, gum arabic
Decomposition product generates adverse effect to coating, and bath stability is not high.
Cadmium plating titanium alloy has the characteristics that technique low hydrogen brittleness, particularly suitable for the anti-of aircraft industry high-tensile structural steel
Sheath.Cadmium plating titanium is all made of for the corrosion-resistant protection of the significant points high-tensile structural steel such as undercarriage both at home and abroad at present
Alloy technology, Boeing Co. use cyanide cadmium titanium alloy technique, and China uses non-cyanide plating cadmium titanium alloy technique.
Summary of the invention
Based on this, it is necessary to provide a kind of no cyanogen cadmium titanium alloy plating solution, and preparation method thereof and electroplating technology, to solve mesh
Preceding no cyanogen cadmium titanium alloy plating solution and quality of coating be not sufficiently stable and electroplating wastewater processing existing for difficulty.
To achieve the above object, the present invention provides the following technical scheme that
Potassium chloride is without cyanogen cadmium titanium alloy plating solution, and plating solution each component and concentration are as follows: 20~35g/L of caddy, complexant 80
~140g/L, 120~200g/L of potassium chloride, 1~5g/L of sodium fluoride, titanium salt feeds 2~5mL/L of agent, brightener 1~3mL/L, auxiliary
20~40mL/L of auxiliary agent, walk 5~15mL/L of agent；
The agent that walks includes water-soluble alkynes propionyl amine polymer, acid dimethyl sodium and polyoxyethylene ether phosphate.
Further, the mass concentration of water-soluble alkynes propionyl amine polymer in agent that walks is 5~15g/L, dimethyl benzene sulphur
The mass concentration of sour sodium is 30~100g/L, and product type is 50~150mL/L of polyoxyethylene ether phosphate of PE 600.
Further, the water-soluble alkynes propionyl amine polymer includes the alkynes propionyl amine polymer containing glucose side group
And/or the alkynes propionyl amine polymer containing lactose side group, the molecular weight of water-soluble alkynes propionyl amine polymer are 10000~15000.
Further, the potassium fluotitanate aqueous solution that titanium salt supply agent is 1.5~2.5g/L of mass concentration.
Further, the complexant includes tri- kinds of components of A, B, C, and wherein component A includes nitrilotriacetic acid, and B component includes
Citric acid, tartaric acid, gluconic acid, any one or two kinds in malic acid, component C includes malonic acid, maleic acid, anti-
Tri- kinds of components of described A, B, C are uniformly mixed and obtain the complexant by any one in butene dioic acid, oxalic acid or two kinds；
The 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 include Vanillin, Veratraldehyde, 4- methoxyl group
Any one in benzaldehyde or two kinds, F component includes propine alcohol ethoxy ether, propilolic alcohol propoxyl group ether, N, N- diethyl third
Ynamine, N, N- diethylpropynyl amine formate, N, any one in N- diethyl propargylamine sulfate or two kinds；
The adjuvant includes the water-soluble polyacrylamide of model IC113,2- ethylhexylsulfate sodium salt, N, N,
It N- tri- (2- hydroxypropyl)-N'- hydroxyethyl ethylenediamine, G component and is made of ethylenediamine, dimethyl propylamine and epoxychloropropane
Condensation product, the G component are consistent with the F component in the brightener.
Further, component A, B component, the ratio of component C in the complexant are as follows: 300~400g, 350~450g of ︰ ︰
250~350g, whole components, which are added to the container, is stirred into complexant；
The configuration proportion of the brightener is: 300mL isopropanol being added in 400mL water and is uniformly mixed, by tri- kinds of D, E and F
Component is dissolved in isopropanol and water mixed liquid by 50~60g, 35~45g and 70~90g respectively, adds water to 1000mL；
The configuration proportion of the adjuvant is: the water-soluble polyacrylamide of 60~70g model IC113,30~40g by
Ethylenediamine, dimethyl propylamine and epoxychloropropane composition condensation product, 50~60g 2- ethylhexylsulfate sodium salt, 15~
(2- the hydroxypropyl)-N'- hydroxyethyl ethylenediamine of 25g N, N, N- tri- and 40~50g G component are added in 700g water, and stirring makes it
Dissolution, then water supplement, to 1000mL, G component is consistent with the F component in brightener.
Preparation method of the potassium chloride without cyanogen cadmium titanium alloy plating solution, steps are as follows:
(1) complexant: component A, B component, the ratio of component C is prepared are as follows: 300~400g, 350~450g of ︰ ︰ 250~
350g, whole components, which are added to the container, to be stirred；
Preparation walks agent: by 5~15g of water-soluble alkynes propionyl amine polymer, 30~100g of acid dimethyl sodium, product type
Number for PE 600 50~150mL of polyoxyethylene ether phosphate be added 500mL water in, add water to 1000mL after mixing evenly；
It prepares brightener: 300mL isopropanol being added in 400mL water and is uniformly mixed, tri- kinds of components of D, E and F are pressed 50 respectively
~60g, 35~45g and 70~90g are dissolved in isopropanol and water mixed liquid, add water to 1000mL；
Formulation aids: the water-soluble polyacrylamide of 60~70g model IC113,30~40g are by ethylenediamine, diformazan
Condensation product, the 50~60g 2- ethylhexylsulfate sodium salt, 15~25g N, N, N- tri- of base propylamine and epoxychloropropane composition
(2- hydroxypropyl)-N'- hydroxyethyl ethylenediamine and 40~50g G component (G component is consistent with the F component in brightener) are added
It in 700g water, stirs to dissolve, then water supplement is to 1000mL；
(2) water of 4/5 aqueduct volume is added into coating bath, sodium hydroxide, potassium chloride, sodium fluoride, complexant, hydrogen-oxygen is added
The mass ratio for changing sodium and complexant is 1 ︰ 2, and sodium hydroxide salt corresponding with the generation of organic acid complexing agent, stirring keeps above-mentioned substance molten
Solution；
(3) caddy is added, stirs to dissolve, filters plating solution；
(4) in 0.05~0.1A/dm2Cathode-current density under be electrolysed 1~8h；
(5) titanium salt is then added and feeds agent, stir evenly；
(6) brightener, adjuvant are sequentially added and the agent that walks, is with the dilute hydrochloric acid or mass fraction that volume ratio is 1 ︰ 1
10% sodium hydroxide solution adjusts the pH value of plating solution to 6.5~7.5, adds water to defined volume, stirs evenly；
Chlorination cadmium concentration reaches 20~35g/L in the plating solution finally obtained, and complexant concentration reaches 80~140g/L, chlorination
Potassium concn reaches 120~200g/L, and concentration of sodium fluoride reaches 1~5g/L, and titanium salt supply agent concentration reaches 2~5mL/L, brightener
Concentration reaches 1~3mL/L, and adjuvant concentration reaches 20~40mL/L, and the agent concentration that walks reaches 5~15mL/L.
Electroplating technology of the potassium chloride without cyanogen cadmium titanium alloy plating solution, comprises the following steps that
(1) workpiece pre-treatment to be plated；
(2) potassium chloride is prepared without cyanogen cadmium titanium alloy plating solution；
(3) it is electroplated, bath pH value is 6.5~7.5 when plating, and coating bath temperature is 20~35 DEG C, and anode is contained using cadmium
The cadmium anode plate of amount >=99.97%；
When using rack plating process, cathode-current density is 0.5~2A/dm2, the ratio between the anode and cathode area are 2 ︰ (1
~3)；
When using barrel plating technique, plating tank voltage is 5~10V, and drum revolving speed is 4~8r/min；
(4) dehydrogenation: plating piece dehydrogenation 12h at 200 DEG C；
(5) the low chromium chromatic passivation of chromate: " it is low that 2% nitric acid goes out light → washing → chromate to the progress of cadmium titanium alloy coating
Chromium chromatic passivation → washing → drying " prepares the low chromium chromatic passivation layer of chromate.
Preferably, it when organic impurity content is excessively high in coating bath, is handled with active carbon, is added 2~4g/L's into plating solution
Active powdered carbon stirs 60~120min, filters plating solution after 2~8h；0.5~1mL/ of brightener is added into plating solution after cleaning filter core
L。
Preferably, it when coating bath is polluted by harmful metal impurity, is handled with electrolysis method, iron material matter cathode is linked into coating bath
The area ratio of plate, cathode and anode is 2 ︰ 1, in 0.05~0.1A/dm21~2h is electrolysed under cathode-current density；Then titanium is added
Salt feeds 1~3mL/L of agent.
Compared with prior art, the invention has the following advantages:
(1) the cadmium titanium alloy plating piece that potassium chloride of the invention is prepared without cyanogen cadmium titanium alloy electroplating technology, according to GB/T
10125-1997 " artificial atmosphere corrosion test salt spray tests " carry out neutral salt spray and test 2800h, cadmium titanium alloy coating redfree
Erosion generates, and corrosion resistance of coating is significantly larger than GB/T 13322-1991 " the crisp cadmium titanium electroplated layer of metal cladding low hydrogen " 500h
Neutral salt spray test does not occur the requirement of red corrosion object；
(2) agent of the present invention that walks can significantly improve the capability of walking of plating solution, expand the range of plating solution current density,
The upper limit of acid non-cyanide plating cadmium process current density is 1.5A/dm in the prior art2, the current density upper limit of the present invention is 2A/dm2,
The current density upper limit 33% is improved compared with ortho acid non-cyanide plating cadmium technique, the plating under higher current density can improve plating solution
Covering power, avoid causing coating coarse problem in high current density region to occur after adding titanium salt supply agent in plating solution, in reality
Production efficiency can also be significantly improved in the production of border；
(3) potassium fluotitanate of the present invention has preferable dissolubility, can be completely dissolved in the plating solution, plating solution will not
There is the sediment of titanium salt hydrolysis；And the TiOCi for using traditional cadmium titanium alloy electroplating technology to use2It then cannot effectively be dissolved in this
The potassium chloride of invention is without in cyanogen cadmium titanium alloy plating solution；
(4) present invention makees the complexant of titanium salt using sodium fluoride, increases the stability that hexafluoro closes titanium complex ion, is plating it
Hydrolysis does not occur in liquid and generates sediment；
(5) present invention prepares brightener and adjuvant using modern electroplating additive intermediate, reduces organic matter in coating
Inclusion content improve the flexibility and corrosion resistance of coating compared with traditional cadmium titanium alloy electroplating technology；
(6) present invention does not use strong complexant (such as EDETATE DISODIUM) to be coordinated cadmium ion, reduces cadmium plating wastewater treatment
Difficulty, wastewater treatment result meet the requirement of GB 21900-2008 " discharge standard for electroplating pollutants " table 3.
Specific embodiment
For a better understanding of the invention, further specific elaboration is made to the present invention below by following embodiment, but not
It can be regarded as limitation of the invention, it is some nonessential according to made by foregoing invention content for those skilled in the art
It improves and adjusts, be also considered as and be within the scope of the present invention.
Embodiment 1:
The potassium chloride of the present embodiment is as follows without cyanogen cadmium titanium alloy plating solution composition and concentration:
Caddy 30g/L, potassium chloride 150g/L, complexant 130g/L, sodium fluoride 3g/L, titanium salt feeds agent 5mL/L, bright
Agent 2mL/L, adjuvant 30mL/L, walk agent 10mL/L；
Mass concentration containing water-soluble alkynes propionyl amine polymer in the agent that walks is 8~12g/L, acid dimethyl
The mass concentration of sodium is 50~80g/L, and product type is 80~120mL/L of polyoxyethylene ether phosphate of PE 600.It will be water-soluble
Property alkynes propionyl amine polymer 8~12g, acid dimethyl sodium mass concentration be 50~80g, product type is the poly- of PE 600
80~120mL of ethylene oxide ether phosphate is added in 500mL water, adds water to 1000mL after mixing evenly.
The complexant is grouped as by tri- kinds of groups of A, B, C, and wherein component A is nitrilotriacetic acid, and B component is by citric acid, winestone
Acid, gluconic acid, any one or two kinds of compositions in malic acid, component C by malonic acid, butadiene dilute acid, the dilute diacid of anti-fourth,
The composition of any one or two kinds in oxalic acid, complexant are prepared in following ratio: A, 300~400g；B, 350~450g；C,250
~350g, is added to the container and is uniformly mixed.
The brightener is grouped as by tri- kinds of groups of D, E, F, and wherein D group is divided into 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 in formaldehyde or two kinds of compositions, F component is by propine alcohol ethoxy ether, propilolic alcohol propoxyl group ether, N, N- diethyl third
Ynamine, N, N- diethylpropynyl amine formate, N, any one or two kinds in N- diethyl propargylamine sulfate are at being grouped as.
Brightener is prepared in following ratio and method: 300mL isopropanol being added in 400mL water and is uniformly mixed, by tri- kinds of components of D, E and F
It is dissolved in isopropanol and water mixed liquid by 50~60g, 35~45g and 70~90g respectively, adds water to 1000mL.
The adjuvant is prepared by the following method: the water-soluble polyacrylamide of 60~70g model IC113,30~
Condensation product that 40g is made of ethylenediamine, dimethyl propylamine and epoxychloropropane, 50~60g 2- ethylhexylsulfate sodium salt,
(2- the hydroxypropyl)-N'- hydroxyethyl ethylenediamine of 15~25g N, N, N- tri- and 40~50g G component are (in G component and brightener
F component is consistent) it is added in 700g water, it stirs to dissolve, then water supplement is to 1000mL.
The titanium salt supply agent is the aqueous solution of potassium fluotitanate, and 2g potassium fluotitanate is dissolved in 800mL water, is added water to
1000mL。
The potassium chloride is prepared by the following method without cyanogen cadmium titanium alloy plating solution:
(1) by the water that 4/5 plating sump volume is added into coating bath, sodium hydroxide, potassium chloride, sodium fluoride and coordination are sequentially added
The mass ratio of agent, sodium hydroxide and complexant is 1 ︰ 2, and stirring dissolves above-mentioned substance；
(2) caddy is then added, and stirs to dissolving, filters plating solution；
(3) in 0.07A/dm2Cathode-current density under be electrolysed 1~8h；
(4) titanium salt is then added and feeds agent, stir evenly；
(5) brightener, adjuvant are sequentially added and the agent that walks, is with the dilute hydrochloric acid or mass fraction that volume ratio is 1 ︰ 1
10% sodium hydroxide solution adjusts the pH to 7 of plating solution, adds water to defined volume, stirs evenly.
Potassium chloride concentration reaches 150g/L, sodium fluoride 3g/L, complexant 130g/L in last plating solution, and titanium salt feeds agent 4mL/
L, caddy 30g/L, brightener 2mL/L, adjuvant 30mL/L, walk agent 10mL/L.
The present embodiment is divided into following steps in concrete operations:
(1) " alkali electroless oil removing → washing → alkalinity anode pre-treatment: is carried out to workpiece to be plated (high strength steel components)
The process of electrolytic degreasing → washing → activation → washing ".
(2) it cadmium plating titanium alloy coating: carries out " potassium chloride being electroplated without cyanogen cadmium titanium alloy → washing after workpiece pre-treatment to be plated
→ drying " prepares cadmium titanium alloy coating.Operating condition when plating is as follows:
Plating solution pH is 6.5~7.5, and coating bath temperature is 25 DEG C, cathode-current density 1.5A/dm2, cathode and annode area
The ratio between be 1 ︰ 1, anode be cadmium content >=99.97% cadmium plate.
(3) dehydrogenation: plating piece dehydrogenation 12h at 200 DEG C.
(4) the low chromium chromatic passivation of chromate: " it is low that 2% nitric acid goes out light → washing → chromate to the progress of cadmium titanium alloy coating
Chromium chromatic passivation → washing → drying " prepares the low chromium chromatic passivation layer of chromate.
It when organic impurity content is excessively high in coating bath, is handled with active carbon, the active carbon of 2~4g/L is added into plating solution
Powder stirs 60~120min, filters plating solution after 2~8h；0.5~1mL/L of brightener is added into plating solution after cleaning filter core.
It when coating bath is polluted by harmful metal impurity, is handled with electrolysis method, iron material matter cathode plate, cathode is linked into coating bath
Area ratio with anode is 2 ︰ 1, in 0.05~0.1A/dm21~2h is electrolysed under cathode-current density；Then titanium salt supply is added
1~3mL/L of agent.
Coating corrosion resistance:
Using the technique preparation plating piece according to GB/T 10125-1997 " artificial atmosphere corrosion test salt spray test " into
Row neutral salt spray tests 3000h, and cadmium titanium alloy coating redfree erosion generates.Cadmium titanium alloy coating manufactured in the present embodiment
500h neutral salt spray test is or not corrosion resistance, significantly larger than GB/T 13322-1991 " the crisp cadmium titanium electroplated layer of metal cladding low hydrogen "
There is the requirement of red corrosion object.
Plating solution covering power:
The thin-walled iron pipe for being 10mm with internal diameter is electroplated in above-mentioned plating solution, anode perpendicular to liquid level, iron pipe inner hole direction with
Anode is parallel, immerses 100mm in plating solution, calculates by external surface area, with 2A/dm2Current density plate 40min, then by sample
It is passivated 10s in low chromium passivating solution, washes, drying.Sample is longitudinally slit, and the length for measuring inner hole coating is 98mm, plating
Layer the ratio between length and aperture are 9.8, and plating solution has good covering power.
Binding force of cladding material:
By JB 2111-1977 " the bonding strength test method of metal cladding ", combined with thermal shock test method measurement coating
Power.Cadmium plating part prepared by the technique is placed in heating furnace and is heated to 190 DEG C, taking-up is put into the water of room temperature to be cooled down suddenly,
Blistering and falling off do not occur in coating, and the cadmium titanium alloy binding force of cladding material is good.
The mass fraction test result of titanium in coating:
267mL hull trough test is carried out without cyanogen cadmium titanium alloy plating solution to prepared potassium chloride, 0.5A electric current plates 40min.With
980 type x-ray fluorescence coating measusre of X-Strata measures the mass fraction of titanium in coating, and acquired results are listed in table 1.Coating
The mass fraction of middle titanium meets the requirement of GB/T 13322-1991 " the crisp cadmium titanium electroplated layer of metal cladding low hydrogen " standard
The mass fraction of titanium in 1 cadmium titanium alloy coating of table
Electroplating wastewater processing:
Cadmium titanium alloy electroplating wastewater sodium dimethyl dithiocarbamate precipitates cadmium ion, cadmium ion after processing
Mass concentration is less than 0.01mg/L, meets the requirement of GB 21900-2008 " discharge standard for electroplating pollutants " table 3.
Embodiment 2:
The barrel plating potassium chloride of the present embodiment is as follows without cyanogen cadmium titanium alloy plating solution composition and concentration:
Caddy 25g/L, potassium chloride 180g/L, complexant 100g/L, sodium fluoride 1g/L, titanium salt feeds agent 2mL/L, bright
Agent 2mL/L, adjuvant 30mL/L, walk agent 5ml/L；
Mass concentration containing water-soluble alkynes propionyl amine polymer in the agent that walks is 5~10g/L, acid dimethyl
The mass concentration of sodium is 70~100g/L, and product type is 100~150mL/L of polyoxyethylene ether phosphate of PE 600.By water
5~10g of dissolubility alkynes propionyl amine polymer, acid dimethyl sodium mass concentration be 70~100g, product type is PE 600
100~150mL of polyoxyethylene ether phosphate be added 500mL water in, add water to 1000mL after mixing evenly.
The complexant, brightener, adjuvant, titanium salt supply agent preparation method are such as embodiment 1.
The potassium chloride is prepared by the following method without cyanogen cadmium titanium alloy plating solution:
(1) water of 4/5 plating sump volume is added into coating bath, sequentially adds sodium hydroxide, potassium chloride, sodium fluoride and coordination
The mass ratio of agent, sodium hydroxide and complexant is 1 ︰ 2, and stirring dissolves above-mentioned substance；
(2) caddy is then added, and stirs to dissolving, filters plating solution；
(3) in 0.08A/dm2Cathode-current density under be electrolysed 1~8h；
(4) titanium salt is then added and feeds agent, stir evenly；
(5) brightener, adjuvant are sequentially added and the agent that walks, is with the dilute hydrochloric acid or mass fraction that volume ratio is 1 ︰ 1
10% sodium hydroxide solution adjusts the pH to 7.5 of plating solution, adds water to defined volume, stirs evenly.
Potassium chloride concentration reaches 180g/L, complexant 100g/L, caddy 25g/L, sodium fluoride 1g/L, titanium in last plating solution
Salt feeds agent 2mL/L, brightener 2mL/L, adjuvant 30mL/L, and walk agent 5mL/L.
The present embodiment is divided into following steps in concrete operations:
(1) " alkali electroless oil removing → washing → sonify pre-treatment: is carried out to workpiece to be plated (high strength steel components)
The process of oil removing → washing → activation → washing ".
(2) barrel plating cadmium titanium alloy coating: " barrel plating potassium chloride is without cyanogen cadmium titanium alloy → washing for progress after workpiece pre-treatment to be plated
→ drying " prepares cadmium titanium alloy coating.Operating condition when plating is as follows:
Plating solution pH is 7.5, and coating bath temperature is 30 DEG C, and plating tank voltage is 6V, and drum revolving speed is 6r/min, and anode is cadmium content
>=99.97% cadmium plate.
(3) dehydrogenation: plating piece dehydrogenation 12h at 200 DEG C.
(4) the low chromium chromatic passivation of chromate: " it is low that 2% nitric acid goes out light → washing → chromate to the progress of cadmium titanium alloy coating
Chromium chromatic passivation → washing → drying " prepares the low chromium chromatic passivation layer of chromate.
It when organic impurity content is excessively high in coating bath, is handled with active carbon, the active carbon of 2~4g/L is added into plating solution
Powder stirs 60~120min, filters plating solution after 2~8h；0.5~1mL/L of brightener is added into plating solution after cleaning filter core.
It when coating bath is polluted by harmful metal impurity, is handled with electrolysis method, iron material matter cathode plate, cathode is linked into coating bath
Area ratio with anode is 2 ︰ 1, in 0.05~0.1A/dm21~2h is electrolysed under cathode-current density；Then titanium salt supply is added
1~3mL/L of agent.
Coating corrosion resistance:
Using the technique preparation plating piece according to GB/T 10125-1997 " artificial atmosphere corrosion test salt spray test " into
Row neutral salt spray tests 2800h, and cadmium titanium alloy coating redfree erosion generates, and coating has excellent corrosion resisting property.
Binding force of cladding material:
By JB 2111-1977 " the bonding strength test method of metal cladding ", combined with thermal shock test method measurement coating
Power.Cadmium plating part prepared by the technique is placed in heating furnace and is heated to 190 DEG C, taking-up is put into the water of room temperature to be cooled down suddenly,
Blistering and falling off do not occur in coating, and the cadmium plating layer binding force is good.
The mass fraction test result, electroplating wastewater processing result of titanium are the same as embodiment 1 in plating solution covering power, coating.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. potassium chloride is without cyanogen cadmium titanium alloy plating solution, which is characterized in that plating solution each component and concentration are as follows: 20~35g/L of caddy,
80~140g/L of complexant, 120~200g/L of potassium chloride, 1~5g/L of sodium fluoride, titanium salt supply 2~5mL/L of agent, brightener 1~
3mL/L, 20~40mL/L of adjuvant, walk 5~15mL/L of agent；
The agent that walks includes water-soluble alkynes propionyl amine polymer, acid dimethyl sodium and polyoxyethylene ether phosphate.
2. potassium chloride as described in claim 1 is without cyanogen cadmium titanium alloy plating solution, it is characterised in that: water-soluble alkynes propionyl in the agent that walks
The mass concentration of amine polymer is 5~15g/L, and the mass concentration of acid dimethyl sodium is 30~100g/L, polyoxyethylene ether
50~150mL/L of phosphate.
3. potassium chloride as claimed in claim 2 is without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
The water solubility alkynes propionyl amine polymer includes the alkynes propionyl amine polymer containing glucose side group and/or containing lactose side
The alkynes propionyl amine polymer of base, the molecular weight of water-soluble alkynes propionyl amine polymer are 10000~15000.
4. potassium chloride as described in claim 1 is without cyanogen cadmium titanium alloy plating solution, it is characterised in that: it is mass concentration that titanium salt, which feeds agent,
The potassium fluotitanate aqueous solution of 1.5~2.5g/L.
5. potassium chloride as described in claim 1 is without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
The complexant includes tri- kinds of components of A, B, C, and wherein component A includes nitrilotriacetic acid, B component include citric acid, tartaric acid,
Any one in gluconic acid, malic acid or two kinds, component C includes malonic acid, maleic acid, fumaric acid, oxalic acid
In any one or two kinds, tri- kinds of components of described A, B, C are uniformly mixed and obtain the complexant；
The 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 in aldehyde or two kinds, F component include propine alcohol ethoxy ether, propilolic alcohol propoxyl group ether, N, N- diethyl propargylamine,
N, N- diethylpropynyl amine formate, N, any one in N- diethyl propargylamine sulfate or two kinds；
The adjuvant includes water-soluble polyacrylamide, 2- ethylhexylsulfate sodium salt, N, N, N- tri- (2- hydroxypropyl)-
N'- hydroxyethyl ethylenediamine, G component and the condensation product being made of ethylenediamine, dimethyl propylamine and epoxychloropropane, the G group
Divide consistent with the F component in the brightener.
6. potassium chloride as claimed in claim 5 is without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
The ratio of component A, B component, component C in the complexant are as follows: 300~400g ︰ 350~450g, 250~350g of ︰, all
Component, which is added to the container, is stirred into complexant；
The configuration proportion of the brightener is: 300mL isopropanol being added in 400mL water and is uniformly mixed, by tri- kinds of components of D, E and F
It is dissolved in isopropanol and water mixed liquid by 50~60g, 35~45g and 70~90g respectively, adds water to 1000mL；
The configuration proportion of the adjuvant is: 60~70g water-soluble polyacrylamide, 30~40g are by ethylenediamine, dimethyl propylamine
With condensation product, the 50~60g 2- ethylhexylsulfate sodium salt, tri- (2- hydroxypropyl of 15~25g N, N, N- of epoxychloropropane composition
Base)-N'- hydroxyethyl ethylenediamine and 40~50g G component be added in 700g water, stir to dissolve, then water supplement is extremely
1000mL, G component are consistent with the F component in brightener.
7. preparation method of the potassium chloride as described in claim 1 without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
Steps are as follows:
(1) complexant: component A, B component, the ratio of component C is prepared are as follows: 300~400g ︰ 350~450g, 250~350g of ︰, entirely
Portion's component, which is added to the container, to be stirred；
Preparation walks agent: by 5~15g of water-soluble alkynes propionyl amine polymer, 30~100g of acid dimethyl sodium, polyoxyethylene ether
50~150mL of phosphate is added in 500mL water, adds water to 1000mL after mixing evenly；
It prepares brightener: 300mL isopropanol being added in 400mL water and is uniformly mixed, tri- kinds of components of D, E and F are pressed 50 respectively~
60g, 35~45g and 70~90g are dissolved in isopropanol and water mixed liquid, add water to 1000mL；
Formulation aids: 60~70g water-soluble polyacrylamide, 30~40g are by ethylenediamine, dimethyl propylamine and epoxychloropropane
The condensation product of composition, 50~60g 2- ethylhexylsulfate sodium salt, 15~25g N, N, N- tri- (2- hydroxypropyl)-N'- hydroxyl second
Base ethylenediamine and 40~50g G component, G component is consistent with the F component in brightener, is added in 700g water, and stirring keeps its molten
Solution, then water supplement is to 1000mL；
(2) water of 4/5 plating sump volume is added into coating bath, sodium hydroxide, potassium chloride, sodium fluoride, complexant, sodium hydroxide is added
Mass ratio with complexant is 1 ︰ 2, and sodium hydroxide salt corresponding with the generation of organic acid complexing agent, stirring dissolves above-mentioned substance；
(3) caddy is added, stirs to dissolve, filters plating solution；
(4) in 0.05~0.1A/dm2Cathode-current density under be electrolysed 1~8h；
(5) titanium salt is then added and feeds agent, stir evenly；
(6) brightener, adjuvant are sequentially added and the agent that walks, is 10% with the dilute hydrochloric acid or mass fraction that volume ratio is 1 ︰ 1
Sodium hydroxide solution adjusts the pH value of plating solution to 6.5~7.5, adds water to defined volume, stirs evenly；
Chlorination cadmium concentration reaches 20~35g/L in the plating solution finally obtained, and complexant concentration reaches 80~140g/L, and potassium chloride is dense
Degree reaches 120~200g/L, and concentration of sodium fluoride reaches 1~5g/L, and titanium salt supply agent concentration reaches 2~5mL/L, brightener concentration
Reach 1~3mL/L, adjuvant concentration reaches 20~40mL/L, and the agent concentration that walks reaches 5~15mL/L.
8. electroplating technology of the potassium chloride as described in claim 1 without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
It comprises the following steps that
(1) workpiece pre-treatment to be plated；
(2) potassium chloride is prepared without cyanogen cadmium titanium alloy plating solution；
(3) be electroplated, bath pH value is 6.5~7.5 when plating, and coating bath temperature is 20~35 DEG C, anode using cadmium content >=
99.97% cadmium anode plate；
When using rack plating process, cathode-current density is 0.5~2A/dm2, the ratio between the anode and cathode area are 2 ︰ (1~3)；
When using barrel plating technique, plating tank voltage is 5~10V, and drum revolving speed is 4~8r/min；
(4) dehydrogenation: plating piece dehydrogenation 12h at 200 DEG C；
(5) the low chromium chromatic passivation of chromate: " it is color that 2% nitric acid goes out the low chromium of light → washing → chromate to the progress of cadmium titanium alloy coating
Color passivation → washing → drying " prepares the low chromium chromatic passivation layer of chromate.
9. electroplating technology of the potassium chloride as claimed in claim 7 without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
It when organic impurity content is excessively high in coating bath, is handled with active carbon, the active powdered carbon of 2~4g/L is added into plating solution, stirs
60~120min is mixed, filters plating solution after 2~8h；0.5~1mL/L of brightener is added into plating solution after cleaning filter core.
10. electroplating technology of the potassium chloride as claimed in claim 7 without cyanogen cadmium titanium alloy plating solution, it is characterised in that:
It when coating bath is polluted by harmful metal impurity, is handled with electrolysis method, iron material matter cathode plate, cathode and sun is linked into coating bath
The area ratio of pole is 2 ︰ 1, in 0.05~0.1A/dm21~2h is electrolysed under cathode-current density；Then add titanium salt supply agent 1~
3mL/L。
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