CN106521610B - A kind of hexavalent chromium plating combination Ni―Ti anode and preparation method thereof - Google Patents
A kind of hexavalent chromium plating combination Ni―Ti anode and preparation method thereof Download PDFInfo
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- CN106521610B CN106521610B CN201611200245.4A CN201611200245A CN106521610B CN 106521610 B CN106521610 B CN 106521610B CN 201611200245 A CN201611200245 A CN 201611200245A CN 106521610 B CN106521610 B CN 106521610B
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
Abstract
The invention discloses a kind of hexavalent chromium plating combination Ni―Ti anodes, including the titanium-based noble metal oxide anode and titanium-based base metal oxide anode being arranged on busbar, and titanium-based noble metal Oxide anode coatings are Ta from the inside to the outside2O5、IrO2‑Ta2O5、IrO2‑Ta2O5‑SnO2And IrO2‑SnO2；Titanium-based base metal oxide anode coating is the PbO of PANI doping2.A kind of preparation method of hexavalent chromium plating combination Ni―Ti anode, titanium-based noble metal oxide anode and titanium-based base metal oxide anode elder generation prepares coating, are then combined, obtain combination Ni―Ti anode.Combination Ni―Ti anode electro catalytic activity height, the resistance to corrosion of the present invention is strong, can work under high current density in hexavalent chromium plating production, and do not generate the earth of positive pole, service life is long.
Description
Technical field
The invention belongs to the anode material technical fields in electrochemical industry, and in particular to a kind of hexavalent chromium plating combination
Ni―Ti anode, the invention further relates to the preparation methods of the combination Ni―Ti anode.
Background technology
Electrochemical industry Anodic material is the component of most critical, this is because：Anode material is the place of anode reaction,
From energy saving and reduce and require that there is high electro-chemical activity and stability to the anode reaction that is catalyzed at seeing originally.Plating
Chromium is a kind of electrochemical method of the deposition chromium on matrix surface, and technics comparing is special, and anode used is insoluble anode, must
Must have higher corrosion resistance and stability.Hexavalent chromium plating solution mainly contains chromic anhybride and sulfuric acid (can also be F-, SiF6-
Ion etc. or other can be catalyzed the anion of chromium plating reaction) two kinds of ingredients, a certain amount of Cr must also be contained in plating solution3+Chromium is heavy
Product can be just normally carried out.Cr3+Presence be on cathode formed colloidal film necessary condition, Cr3+Optimum content depend on plating solution
Composition and process conditions, generally 2g/L~5g/L, no more than 10g/L.In addition, the current density of electrodeposited chromium generally use
It is relatively high, it is tens times higher than the current density of general plating, it is therefore desirable to which that anode material must satisfy long-time high current density
Under job requirement.
Using lead or alloy lead anode in existing hexavalent chromium plating production, although the cost of this anode is relatively low,
But lead anode, which is easy to react with chromic acid, produces plumbous chromate, and with the progress of anode reaction, plumbous chromate can fall off shape from anode surface
At a large amount of earth of positive pole, plating solution is polluted, various plating defects are brought；Secondly as the plumbous chromate of a large amount of poorly conductives is covered in sun
Pole surface seriously affects anode conductivity, it is therefore desirable to periodically carry out grinding process to anode surface, this not only results in anode
A large amount of losses, and the lead powder dirt generated seriously affects environment；In addition, service life of the lead anode in electrodeposited chromium production compares
It is short, it can only generally work 6 months, and need within every 2 months to clear up an earth of positive pole.To solve the above-mentioned problems, titanium-based size
Stability anode is introduced in plating chromium process, includes mainly Ti/IrO2-Ta2O5Anode and Ti/PbO2Anode.
Ti/IrO2-Ta2O5Anode has good electro catalytic activity and stability in acidic environment, and is being electrolysed
The dissolving of journey floating coat is fairly small to be ignored, and pollution, long lifespan, when can be long at higher current densities will not be generated to plating solution
Between work, Titanium base can also reuse.But relative to lead anode, traditional Ti/IrO2-Ta2O5The oxygen evolution potential of anode
It is too low, due to Cr3+Oxidizing potential it is higher than the deposition potential of oxygen, so anode reaction is unfavorable for Cr when oxygen evolution potential is too low3+To
Cr6+Conversion, lead to Cr in plating solution3+Concentration is higher and higher, influences quality of coating.Ti/PbO2Anode electricity in acidic environment is urged
It is high to change activity, overpotential for oxygen evolution is high, to Cr in plating solution3+To Cr6+Conversion reaction have facilitation.But traditional Ti/
PbO2Anode stability is poor, and failure mechanism is exactly the dissolving of brown lead oxide, especially continuous work at higher current densities
It can accelerate its dissolving, pollution is generated to plating solution.Therefore, how to develop and have both stable Cr3+Ion concentration and avoid pollution plating solution work(
The anode material of energy, is exactly current hexavalent chromium plating industry urgent problem to be solved.
Invention content
The object of the present invention is to provide a kind of hexavalent chromium plating combination Ni―Ti anodes, can control Cr in plating solution3+Concentration.
It is a further object to provide a kind of hexavalent chromium plating preparation methods of combination Ni―Ti anode.
The technical solution adopted in the present invention is a kind of hexavalent chromium plating combination Ni―Ti anode, including is arranged at intervals on and leads
Electricity row on titanium-based noble metal oxide anode and titanium-based base metal oxide anode, titanium-based noble metal Oxide anode coatings by
Interior to outer is Ta2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2；Titanium-based base metal oxide anode coating is
The PbO of PANI doping2。
The features of the present invention also characterized in that：
The quantity ratio of titanium-based noble metal oxide anode and titanium-based base metal oxide anode is 3:1~1:3.
Another technical solution of the present invention is a kind of preparation method of hexavalent chromium plating combination Ni―Ti anode,
Include the following steps；
Step 1, titanium-based material burn plating Ta successively after pre-treatment2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-
SnO2It is made and contains cated titanium-based noble metal oxide anode, another titanium-based material first burns plating SnO after pre-treatment2-
Sb2O5, the PbO of re-plating PANI doping2Layer is made containing cated titanium-based base metal oxide anode；
Step 1 is made containing cated titanium-based noble metal oxide anode and titanium-based base metal oxide anode step 2
With quantity ratio for 3 on busbar:1~1:3 carry out being alternatively arranged combination, obtain combination Ni―Ti anode.
The features of the present invention also characterized in that
It is made in step 1 and is specially containing cated titanium-based noble metal oxide anode；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then through boiling
Pickling at least 1h removes descale in oxalic acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying waits for
With；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, will use
It is configured to masking liquid in dissolving noble metal precursor body；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C
Dry 10min repeats above-mentioned coating-drying-roasting 1~3 time, obtains containing Ta then at 500 DEG C of roasting 15min2O5Coating
Titanium-based material；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step
On rapid 3 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 3~5 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With 3.6g/L SnCl4N-butanol-isopropanol it is mixed
It closes liquid to be coated on the titanium-based material that step 4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned painting
- roasting 2~4 times is covered-dried, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2Coating
Titanium-based material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On rapid 5 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 1~3 time, obtains being Ta from the inside to the outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The expensive gold of titanium-based of coating
Belong to oxide anode.
It is made in step 1 and is specially containing cated titanium-based base metal oxide anode；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the grass through boiling
Pickling at least 1h removes descale in acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, are used for
Dissolving base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is applied with n-butanol-isopropanol mixed liquor of 0.05g/L HCl
It is overlying on the Titanium base of drying, above-mentioned coating-drying-roasting is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It burns 5 times, obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 0.2~2g/L An mixing water
Solution is added in electrodeposit reaction device, controls 60~70 DEG C of bath temperature, and mixing speed is 500~1000r/min；Then with
The titanium-based material that step 3 obtains is anode, and two pieces of Titanium bases of same area are placed respectively with anode both sides as cathode, control
Current density is 100~400A/m2, electrodeposit reaction is carried out, sedimentation time is controlled in 2~8h, obtains adulterating PbO containing PANI2
The titanium-based base metal oxide anode of coating.
The invention has the advantages that
(1) a type sandwich-like structure titanium-based noble metal oxide anode is proposed.The Ni―Ti anode feature of this structure
It is that protective layer Ta is sequentially depositing on anode base material2O5, active layer IrO2-Ta2O5, active layer IrO2-Ta2O5-SnO2And activity
Layer IrO2-SnO2。Ta2O5Corrosion resistance it is very strong, introduce Ta on titanium-based material2O5Layer can effectively improve the use longevity of anode
Life；SnO2Introducing can improve the oxygen evolution potential of electrode, to Cr3+To Cr6+Conversion have certain facilitation.
(2) a kind of PbO of titanium-based PANI doping is proposed2Anode.PANI is a kind of corrosion-resistant, resistance to oxidation conducting polymer
Object is entrained in PbO2The internal stress that brown lead oxide can not only be disperseed in sedimentary, can also improve the corrosion-resistant of coating
Property, extend its service life.
(3) combination Ni―Ti anode prepared by the present invention is nearly free from the earth of positive pole in electrodeposited chromium production, and bath stability is good.
It (4) can be by adjusting the number of combinations of noble metallic oxide anode and anode of lead dioxide ratio in combination Ni―Ti anode
Example controls Cr in plating solution3+Concentration.
(5) the combination Ni―Ti anode prepared using the present invention temperature can be worked at higher current densities, and service life can
Reach 15 months or more.
Description of the drawings
Fig. 1 is the structural schematic diagram that a kind of hexavalent chromium plating of the present invention combines Ni―Ti anode；
Fig. 2 is titanium-based noble metal oxide anode and remaining two kinds of titanium-based noble metal oxide prepared by the method for the present invention
Oxygen evolution potential test result figure of the anode in 0.5M sulfuric acid；
Fig. 3 is titanium-based base metal oxide anode and remaining two kinds of titanium-based base metal oxide prepared by the method for the present invention
Reinforcing life test result figure of the anode in 1M sulfuric acid solutions.
In figure, 1. busbars, 2. titanium-based noble metal oxide anodes, 3. titanium-based base metal oxide anodes.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The present invention provides a kind of hexavalent chromium plating combination Ni―Ti anodes, as shown in Figure 1, including being arranged at intervals on busbar
Titanium-based noble metal oxide anode 2 on 1 and titanium-based base metal oxide anode 3,2 coating of titanium-based noble metal oxide anode by
Interior to outer is Ta2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2；3 coating of titanium-based base metal oxide anode
It is the PbO of PANI doping2；
The quantity ratio of titanium-based noble metal oxide anode 2 and titanium-based base metal oxide anode 3 is 3:1~1:3.
A kind of hexavalent chromium plating preparation method of combination Ni―Ti anode, includes the following steps；
Step 1, titanium-based material burn plating Ta successively after pre-treatment2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-
SnO2It is made and contains cated titanium-based noble metal oxide anode 2, another titanium-based material first burns plating SnO after pre-treatment2-
Sb2O5, the PbO of re-plating PANI doping2Layer is made containing cated titanium-based base metal oxide anode 3；
It is made in step 1 and is specially containing cated titanium-based noble metal oxide anode 2；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then through boiling
Pickling at least 1h removes descale in oxalic acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying waits for
With；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, will use
It is configured to masking liquid in dissolving noble metal precursor body；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C
Dry 10min repeats above-mentioned coating-drying-roasting 1~3 time, obtains containing Ta then at 500 DEG C of roasting 15min2O5Coating
Titanium-based material；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step
On rapid 3 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 3~5 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With 3.6g/L SnCl4N-butanol-isopropanol it is mixed
It closes liquid to be coated on the titanium-based material that step 4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned painting
- roasting 2~4 times is covered-dried, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2Coating
Titanium-based material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On rapid 5 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 1~3 time, obtains being Ta from the inside to the outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The expensive gold of titanium-based of coating
Belong to oxide anode 2；
It is made in step 1 and is specially containing cated titanium-based base metal oxide anode 3；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the grass through boiling
Pickling at least 1h removes descale in acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, are used for
Dissolving base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is applied with n-butanol-isopropanol mixed liquor of 0.05g/L HCl
It is overlying on the Titanium base of drying, above-mentioned coating-drying-roasting is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It burns 5 times, obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 0.2~2g/L An mixing water
Solution is added in electrodeposit reaction device, controls 60~70 DEG C of bath temperature, and mixing speed is 500~1000r/min；Then with
The titanium-based material that step 3 obtains is anode, and two pieces of Titanium bases of same area are placed respectively with anode both sides as cathode, control
Current density is 100~400A/m2, electrodeposit reaction is carried out, sedimentation time is controlled in 2~8h, obtains adulterating PbO containing PANI2
The titanium-based base metal oxide anode 3 of coating；
Step 1 is made containing cated titanium-based noble metal oxide anode 2 and titanium-based base metal oxide sun step 2
Pole 3 is on busbar 1 with quantity ratio for 3:1~1:3 carry out being alternatively arranged combination, obtain combination Ni―Ti anode.
Ni―Ti anode is combined for the hexavalent chromium plating field in electrochemical industry.
As shown in Fig. 2, Fig. 2 (a) is the IrO2-Ta2O5 anodes (Ti/IrO2-Ta2O5) directly coated on titanium-based material；(b)
For the class sandwich structure sun of Ta2O5, IrO2-Ta2O5, IrO2-Ta2O5-SnO2 and IrO2-SnO2 are coated on titanium-based material successively
Pole (Ti/Ta2O5/IrO2-Ta2O5/IrO2-Ta2O5-SnO2/IrO2-SnO2) shows class sandwich structure anode from Fig. 2
Oxygen evolution potential effectively improved；
As shown in figure 3, Fig. 3 (a) is traditional titanium-based PbO2 anodes (Ti/PbO2)；(b) it is the titanium-based PbO2 of PANI doping
Anode (Ti/PANI-PbO2), the PbO2 anodes after showing PANI doping in Fig. 3 are with longer service life.
Embodiment 1
A kind of hexavalent chromium plating preparation method of combination Ni―Ti anode, includes the following steps；
Step 1, system are specially containing cated titanium-based noble metal oxide anode 2；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then through boiling
Pickling at least 1h removes descale in oxalic acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying waits for
With；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, is used for
Dissolving noble metal precursor body is configured to masking liquid；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C
Dry 10min repeats above-mentioned coating-drying-roasting 3 times, obtains containing Ta then at 500 DEG C of roasting 15min2O5The titanium of coating
Base material；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step
On rapid 3 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 5 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With the SnCl of 3.6g/L4N-butanol-isopropanol mixing
Liquid is coated on the titanium-based material that step 4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned painting
- roasting 2 times is covered-dried, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2The titanium-based of coating
Material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On rapid 5 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 2 times, obtains being Ta from the inside to the outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The titanium-based noble metal oxygen of coating
Compound anode 2, is marked as A1；
It makes containing cated titanium-based base metal oxide anode 3 and is specially；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the grass through boiling
Pickling at least 1h removes descale in acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, are used for
Dissolving base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is applied with n-butanol-isopropanol mixed liquor of 0.05g/L HCl
It is overlying on the Titanium base of drying, above-mentioned coating-drying-roasting is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It burns 5 times, obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 2g/L An mixed aqueous solution add
Enter into electrodeposit reaction device, controls 60 DEG C of bath temperature, mixing speed 1000r/min；Then the titanium-based obtained with step 2
Material is anode, two pieces of Titanium bases of same area is placed respectively with anode both sides as cathode, control current density is 100A/
m2, electrodeposit reaction is carried out, sedimentation time is controlled in 8h, obtains adulterating PbO containing PANI2The titanium-based base metal oxide of coating
Anode 3, is marked as B1；
Step 2, by A1 and B1 with 1:1 ratio is combined to obtain combination Ni―Ti anode P1.
Embodiment 2
Embodiment 2 is same as Example 1, wherein the difference is that：The portfolio ratio of the A1 and B1 is 3:1, it obtains
Combine Ni―Ti anode P2.
Embodiment 3
Embodiment 3 is same as Example 1, wherein the difference is that：The portfolio ratio of the A1 and B1 is 3:1, it obtains
Combine Ni―Ti anode P3.
Embodiment 4
A kind of hexavalent chromium plating preparation method of combination Ni―Ti anode, includes the following steps；
Step 1, system are specially containing cated titanium-based noble metal oxide anode 2；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then through boiling
Pickling at least 1h removes descale in oxalic acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying waits for
With；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, is used for
Dissolving noble metal precursor body is configured to masking liquid；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C
Dry 10min is obtained then at 500 DEG C of roasting 15min containing Ta2O5The titanium-based material of coating；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step
On rapid 3 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 4 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With the SnCl of 3.6g/L4N-butanol-isopropanol mixing
Liquid is coated on the titanium-based material that step 4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned painting
- roasting 4 times is covered-dried, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2The titanium-based of coating
Material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On rapid 5 obtained titanium-based materials, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min, obtain being Ta from the inside to the outside2O5、
IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The titanium-based noble metal oxide anode 2 of coating, is marked as A2；
It makes containing cated titanium-based base metal oxide anode 3 and is specially；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the grass through boiling
Pickling at least 1h removes descale in acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, are used for
Dissolving base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is applied with n-butanol-isopropanol mixed liquor of 0.05g/L HCl
It is overlying on the Titanium base of drying, above-mentioned coating-drying-roasting is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It burns 5 times, obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 1g/L An mixed aqueous solution add
Enter into electrodeposit reaction device, controls 65 DEG C of bath temperature, mixing speed 800r/min；Then the titanium-based obtained with step 2
Material is anode, two pieces of Titanium bases of same area is placed respectively with anode both sides as cathode, control current density is 200A/
m2, electrodeposit reaction is carried out, sedimentation time is controlled in 4h, obtains adulterating PbO containing PANI2The titanium-based base metal oxide of coating
Anode 3, is marked as B2；
Step 2, by A2 and B2 with 1:1 ratio is combined to obtain combination Ni―Ti anode P4.
Embodiment 5
Embodiment 5 is same as Example 4, wherein the difference is that：The portfolio ratio of the A2 and B2 is 3:1, it obtains
Combine Ni―Ti anode P5.
Embodiment 6
Embodiment 6 is same as Example 4, wherein the difference is that：The portfolio ratio of the A2 and B2 is 3:1, it obtains
Combine Ni―Ti anode P6.
Embodiment 7
A kind of hexavalent chromium plating preparation method of combination Ni―Ti anode, includes the following steps；
Step 1, system are specially containing cated titanium-based noble metal oxide anode 2；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then through boiling
Pickling at least 1h removes descale in oxalic acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying waits for
With；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, is used for
Dissolving noble metal precursor body is configured to masking liquid；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C
Dry 10min repeats above-mentioned coating-drying-roasting 2 times, obtains containing Ta then at 500 DEG C of roasting 15min2O5The titanium of coating
Base material；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step
On rapid 3 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 3 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With the SnCl of 3.6g/L4N-butanol-isopropanol mixing
Liquid is coated on the titanium-based material that step 4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned painting
- roasting 3 times is covered-dried, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2The titanium-based of coating
Material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On rapid 5 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 3 times, obtains being Ta from the inside to the outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The titanium-based noble metal oxygen of coating
Compound anode 2, is marked as A3；
It makes containing cated titanium-based base metal oxide anode 3 and is specially；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the grass through boiling
Pickling at least 1h removes descale in acid solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, are used for
Dissolving base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is applied with n-butanol-isopropanol mixed liquor of 0.05g/L HCl
It is overlying on the Titanium base of drying, above-mentioned coating-drying-roasting is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It burns 5 times, obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 0.2g/L An mixed aqueous solution
It is added in electrodeposit reaction device, controls 70 DEG C of bath temperature, mixing speed 500r/min；Then the titanium obtained with step 2
Base material is anode, two pieces of Titanium bases of same area is placed respectively with anode both sides as cathode, control current density is
400A/m2, electrodeposit reaction is carried out, sedimentation time is controlled in 4h, obtains adulterating PbO containing PANI2The titanium-based base metal oxygen of coating
Compound anode 3, is marked as B3；
Step 2, by A3 and B3 with 1:1 ratio is combined to obtain combination Ni―Ti anode P7.
Embodiment 8
Embodiment 8 is same as Example 1, wherein the difference is that：The portfolio ratio of the A3 and B3 is 3:1, it obtains
Combine Ni―Ti anode P8.
Embodiment 9
Embodiment 9 is same as Example 1, wherein the difference is that：The portfolio ratio of the A3 and B3 is 3:1, it obtains
Combine Ni―Ti anode P9.
Performance test
Hexavalent chromium plating performance test is carried out to combination Ni―Ti anode (P1, P2, P3) prepared by the embodiment of the present invention 1,2,3,
Method is：Ni―Ti anode stainless steel cathode similar with area will be combined with 2:1 ratio is put into from hexavalent chromium plating producer and fetches
Plating solution in (Cr after testing3+A concentration of 3.2g/L), electroplating experiments are carried out by DC power supply, bath temperature is 65 DEG C, cloudy
Electrode current density is 1500A/m2, respectively its voltage and Cr are monitored after being electroplated 1 day, 3 days, 7 days, 15 days and 30 days3+Concentration
Value, the results are shown in Table 1.
1 combined anode hexavalent chromium plating the performance test results of table
As can be seen from Table 1, combination Ni―Ti anode prepared by the method for the present invention works during hexavalent chromium plating
Voltage stabilization, voltage only increases 0.1~0.2V after continuous work 1 month；In addition, Cr3+Concentration can be in continuous work 1
Reach stable after week, and concentration value is within the scope of demand of industrial production.Above two important parameters show prepared by the present invention
Combine Ni―Ti anode has good chemical property during hexavalent chromium plating.
Claims (4)
1. a kind of hexavalent chromium plating combination Ni―Ti anode, which is characterized in that the titanium-based including being arranged at intervals on busbar (1) is expensive
Metal oxide anode (2) and titanium-based base metal oxide anode (3), the titanium-based noble metal oxide anode (2) and titanium-based
The quantity ratio of base metal oxide anode (3) is 3:1~1:3, titanium-based noble metal oxide anode (2) coating is from the inside to the outside
Ta2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2；Titanium-based base metal oxide anode (3) coating is first to burn
Plate SnO2-Sb2O5, the PbO of re-plating PANI doping2Layer.
2. a kind of hexavalent chromium plating as described in claim 1 preparation method of combination Ni―Ti anode, which is characterized in that including with
Lower step；
Step 1, titanium-based material burn plating Ta successively after pre-treatment2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2System
At containing cated titanium-based noble metal oxide anode (2), another titanium-based material first burns plating SnO after pre-treatment2-Sb2O5, then
The PbO of PANI doping is electroplated2Layer is made containing cated titanium-based base metal oxide anode (3)；
Step 1 is made containing cated titanium-based noble metal oxide anode (2) and titanium-based base metal oxide anode step 2
(3) on busbar (1) with quantity ratio be 3:1~1:3 carry out being alternatively arranged combination, obtain combination Ni―Ti anode.
3. a kind of preparation method of hexavalent chromium plating combination Ni―Ti anode according to claim 2, which is characterized in that
It is made in the step 1 and is specially containing cated titanium-based noble metal oxide anode (2)；
Step 1.1, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the oxalic acid through boiling
Pickling at least 1h removes descale in solution, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Step 1.2, by n-butanol and isopropanol with volume ratio 1:1 is mixed and made into n-butanol-isopropyl alcohol mixed solvent, will be used for molten
Solution noble metal precursor body is configured to masking liquid；
Step 1.3, by 20g/L TaCl5N-butanol-isopropanol masking liquid be coated on drying Titanium base on, in 120 DEG C of dryings
10min repeats above-mentioned coating-drying-roasting 1~3 time, obtains containing Ta then at 500 DEG C of roasting 15min2O5The titanium of coating
Base material；
Step 1.4 will contain 39.5g/L H2IrCl6With 10g/L TaCl5N-butanol-isopropanol mixed liquor be coated on step 1.3
On obtained titanium-based material, above-mentioned coating-drying-roasting 3 is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It~5 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5The titanium-based material of coating；
Step 1.5 will contain 39.5g/L H2IrCl6、5g/L TaCl5With 3.6g/L SnCl4N-butanol-isopropanol mixed liquor apply
It is overlying on the titanium-based material that step 1.4 obtains, in 120 DEG C of dry 10min, then at 500 DEG C of roasting 15min；Repeat above-mentioned coating-
Drying-roasting 2~4 times, obtains containing Ta successively from inside to outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2The titanium-based of coating
Material；
Step 1.6 will contain 39.5g/L H2IrCl6With 7.2g/L SnCl4N-butanol-isopropanol mixed liquor be coated on step
On 1.5 obtained titanium-based materials, above-mentioned coating-drying-roasting is repeated then at 500 DEG C of roasting 15min in 120 DEG C of dry 10min
It burns 1~3 time, obtains being Ta from the inside to the outside2O5、IrO2-Ta2O5、IrO2-Ta2O5-SnO2And IrO2-SnO2The expensive gold of titanium-based of coating
Belong to oxide anode (2).
4. a kind of preparation method of hexavalent chromium plating combination Ni―Ti anode according to claim 2, which is characterized in that described
It is made in step 1 and is specially containing cated titanium-based base metal oxide anode (3)；
The first step, titanium-based material are put into the NaOH solution of 10wt% after sandblasting and boil alkali cleaning oil removing, then the oxalic acid through boiling is molten
Pickling at least 1h removes descale in liquid, and after finally using tap water, deionized water and alcohol to clean successively, drying is for use；
Second step, by n-butanol and isopropanol with volume ratio 1:5 are mixed and made into n-butanol-isopropyl alcohol mixed solvent, for dissolving
Base metal presoma is configured to masking liquid；
Third step will contain 60g/L SnCl4、3g/L SbCl3It is coated on n-butanol-isopropanol mixed liquor of 0.05g/L HCl
On the Titanium base of drying, above-mentioned coating-drying-roasting 5 is repeated then at 450 DEG C of roasting 10min in 120 DEG C of dry 10min
It is secondary, it obtains containing SnO2-Sb2O5The titanium-based material of coating；
4th step will contain 150g/L Pb (NO3)2、6g/L HNO3, 0.3g/L NaF and 0.2~2g/L An mixed aqueous solution
It is added in electrodeposit reaction device, controls 60~70 DEG C of bath temperature, mixing speed is 500~1000r/min；Then with third
It is anode to walk obtained titanium-based material, and two pieces of Titanium bases of same area are placed respectively with anode both sides as cathode, control electricity
Current density is 100~400A/m2, electrodeposit reaction is carried out, sedimentation time is controlled in 2~8h, obtains adulterating PbO containing PANI2It applies
The titanium-based base metal oxide anode (3) of layer.
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