CN106560530A - High titanium alloy bonding strength lead dioxide electroplating process - Google Patents

High titanium alloy bonding strength lead dioxide electroplating process Download PDF

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Publication number
CN106560530A
CN106560530A CN201610992939.XA CN201610992939A CN106560530A CN 106560530 A CN106560530 A CN 106560530A CN 201610992939 A CN201610992939 A CN 201610992939A CN 106560530 A CN106560530 A CN 106560530A
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China
Prior art keywords
electroplating
nickel
titanium alloy
matrix
anode
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Pending
Application number
CN201610992939.XA
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Chinese (zh)
Inventor
张永春
秦少军
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Baoji University of Arts and Sciences
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Baoji University of Arts and Sciences
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Priority to CN201610992939.XA priority Critical patent/CN106560530A/en
Publication of CN106560530A publication Critical patent/CN106560530A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes

Abstract

The invention discloses a high titanium alloy bonding strength lead dioxide electroplating process, which comprises acid washing, anode activation, drying, heat treatment, acid washing, low stress nickel electroplating, anode electroplating of lead dioxide, and water washing. According to the present invention, based on the electroplating pre-treatment and the electroplating process, a series of problems comprise that the process can achieve the high nickel middle layer and matrix titanium or titanium alloy bonding strength and the close bonding, the electroplating of the low stress nickel middle layer reduces the influence of the middle layer stress on the lead dioxide plating layer breaking and shedding, and the like are researched, such that finally the firm bonding and breaking-resistant lead dioxide plating layer is obtained on the titanium and titanium alloy surface, and the application industry range is expanded.

Description

A kind of titanium alloy high bond strength electroplates brown lead oxide technique
Technical field
The present invention relates to active metal alloy surface treatment and electroplating technology field, and in particular to a kind of titanium alloy is high to be combined Intensity electroplates brown lead oxide technique.
Background technology
In titanium or titanium alloy electroplating surface brown lead oxide, primarily to obtaining a kind of high catalytic activity and corrosion resistant electricity Pole material.The preparation of current ti-supported lead dioxide electric pole material mainly using plating, but due to lead dioxide plating coat with Lead dioxide plating coat easily occurs what is fractured and flaked off due to due to stress and matrix are oxidizable between titanium or titanium alloy matrix Phenomenon.This is also the main cause for limiting ti-supported lead dioxide electric pole service life.
The content of the invention
It is an object of the invention to provide a kind of titanium alloy high bond strength electroplates brown lead oxide technique, titanium and titanium are solved The coating rupture that stress and adhesion cause between alloy substrate and coating and the problem for coming off, finally give titanium or titanium alloy Matrix is firmly combined with and does not have apertured ti-supported lead dioxide electric pole with lead dioxide plating coat, extends its service life and spreads it Application industry scope.
For achieving the above object, the technical scheme taken of the present invention is：
A kind of titanium alloy high bond strength electroplates brown lead oxide technique, comprises the steps：
S1, pickling
With the hydrofluoric acid 50-70ml/L that mass fraction is 40%, nitric acid 280-320ml/L, the fluorine that mass fraction is 65% The solution that change sodium 2-15g/L the is made into pure titanium of pickling or titanium alloy 50s under 25-45 DEG C of temperature conditionss；
S2, anode activation
Anode activation is carried out to the pure titanium or titanium alloy obtained by step S1 using pulse current, its process conditions is：Sulfuric acid Nickel 60-100g/L, nickel chloride 30-50g/L, trisodium citrate 5-15g/L, boric acid 25-40g/L, anode active additive 20- 50g/L；Anode average current density 2-5A/dm-2, pH=3-4, T=50-60 DEG C, t=1-5min；Then anode, negative electrode are switched The sense of current carries out negative electrode electro-deposition zinc, negative electrode average current density 1-3A/dm-2, electroplating time 0.5-5min；
S3, cleaning, drying
After matrix after anode activation is cleaned with flowing water, the heating, drying at 100-300 DEG C；
S4, heat treatment
Under T=100-500 DEG C, the process conditions of pressure 1-100MPa, t=0.1-5h to drying after matrix carry out heat Process；
S5, pickling
Oxide and the activation that heat treatment process matrix surface is produced is removed using pickling, its process conditions is：Quality point Number is 65% nitric acid 20-40ml/L, sulfuric acid 10-30ml/L, T=20-45 DEG C that mass fraction is 98%, electroplating time 2- 6s；
S6, electroplating of low-stress nickel
Electroplating of low-stress nickel is carried out to the matrix after pickling using nickel sulfamic acid, its process conditions is：Sulfamic acid Nickel 250-300g/L, boric acid 20-30g/L, nickel chloride 10-25g/L, pH=3-4, T=45-65 DEG C, cathode-current density 2-5A/ dm-2, electroplating time 2-10min；
S7, anodization brown lead oxide
Matrix Anodic after electroplating of low-stress nickel electroplates brown lead oxide, and its process conditions is：Plumbi nitras 250-300g/ L, red fuming nitric acid (RFNA) 15-20g/L, sodium fluoride 0.2-1g/L, T=50-70 DEG C, anodic current density 0.02-0.15A/dm-2, plating when Between 0.5-10h, air burst agitation；
S8, washing
Matrix after to electroplating brown lead oxide carries out washing and dries naturally.
Preferably, the anode active additive is gelatin.
The invention has the advantages that：
Service life of the ti-supported lead dioxide electric pole material in electrolytic zinc simulated test is significantly improved, stress and The rupture obscission that matrix oxidation causes disappears substantially.
Description of the drawings
Fig. 1 is the preparation flow that embodiment of the present invention titanium alloy high bond strength electroplates intermediate layer in brown lead oxide technique Figure.
Specific embodiment
In order that objects and advantages of the present invention become more apparent, the present invention is carried out further with reference to embodiments Describe in detail.It should be appreciated that specific embodiment described herein is not used to limit this only to explain the present invention It is bright.
Embodiment
Step one, it is 40% hydrofluoric acid 50-70ml/L, the nitric acid 280- that mass fraction is 65% with mass fraction The solution that 320ml/L, sodium fluoride 2-15g/L are made under 25-45 DEG C of temperature conditionss pickling to the pure titaniums of TA2 after polishing and oil removing Plate 50s,.
Step 2, in nickel sulfate 60-100g/L, nickel chloride 30-50g/L, trisodium citrate 5-15g/L, boric acid 25-40g/ L, anode active additive 20-50g/L, anode average current density 2-5A/dm-2, pH=3-4, T=50-60 DEG C, electrolyte Anodic activates 1-5min；Then switching anode, cathode current direction carries out negative electrode electro-deposition zinc, negative electrode average current density 1- 3A/dm-2, electroplating time 0.5-5min；The anode active additive is gelatin；
Step 3 and then the matrix cleaned after anode activation with flowing water, the then heating, drying at 100-300 DEG C
Step 4, to dry matrix carry out under the conditions of T=100-500 DEG C, pressure 1-100MPa heat treatment 0.1-5h, Slow cooling.
Step 5, to cool down matrix in the nitric acid 20-40ml/L, the sulphur that mass fraction is 98% that mass fraction is 65% Sour 10-30ml/L, T=20-45 DEG C electricity price also middle etch 2-6s.
Step 6, the matrix to etch are made in nickel sulfamic acid 250-300g/L, boric acid 20-30g/L, nickel chloride 10- Electroplating of low-stress nickel in 25g/L, pH=3-4, T=45-65 DEG C of electrolyte, cathode-current density 2-5A/dm-2, electroplating time 2-10min。
Matrix after step 7, electroplating of low-stress nickel is in plumbi nitras 250-300g/L, red fuming nitric acid (RFNA) 15-20g/L, sodium fluoride 0.2-1g/L, T=50-70 DEG C, plating brown lead oxide, anodic current density 0.02-0.15A/dm-2, electroplating time 0.5-10h, Air burst agitation.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (2)

1. a kind of titanium alloy high bond strength electroplates brown lead oxide technique, it is characterised in that：Comprise the steps：
S1, pickling
With the hydrofluoric acid 50-70ml/L that mass fraction is 40%, nitric acid 280-320ml/L, the sodium fluoride that mass fraction is 65% The solution that 2-15g/L the is made into pure titanium of pickling or titanium alloy 50s under 25-45 DEG C of temperature conditionss；
S2, anode activation
Anode activation is carried out to the pure titanium or titanium alloy obtained by step S1 using pulse current, its process conditions is：Nickel sulfate 60- 100g/L, nickel chloride 30-50g/L, trisodium citrate 5-15g/L, boric acid 25-40g/L, anode active additive 20-50g/L； Anode average current density 2-5A/dm-2, pH=3-4, T=50-60 DEG C, t=1-5min；Then anode, cathode current side are switched To carrying out negative electrode electro-deposition zinc, negative electrode average current density 1-3A/dm-2, electroplating time 0.5-5min；
S3, cleaning, drying
After matrix after anode activation is cleaned with flowing water, the heating, drying at 100-300 DEG C；
S4, heat treatment
Under T=100-500 DEG C, the process conditions of pressure 1-100MPa, t=0.1-5h to drying after matrix carry out hot place Reason；
S5, pickling
Oxide and the activation that heat treatment process matrix surface is produced is removed using pickling, its process conditions is：Mass fraction is 65% nitric acid 20-40ml/L, sulfuric acid 10-30ml/L, T=20-45 that mass fraction is 98% DEG C, electroplating time 2-6s；
S6, electroplating of low-stress nickel
Electroplating of low-stress nickel is carried out to the matrix after pickling using nickel sulfamic acid, its process conditions is：Nickel sulfamic acid 250-300g/L, boric acid 20-30g/L, nickel chloride 10-25g/L, pH=3-4, T=45-65 DEG C, cathode-current density 2-5A/ dm-2, electroplating time 2-10min；
S7, anodization brown lead oxide
Matrix Anodic after electroplating of low-stress nickel electroplates brown lead oxide, and its process conditions is：It is plumbi nitras 250-300g/L, dense Nitric acid 15-20g/L, sodium fluoride 0.2-1g/L, T=50-70 DEG C, anodic current density 0.02-0.15A/dm-2, electroplating time 0.5-10h, air burst agitation；
S8, washing
Matrix after to electroplating brown lead oxide carries out washing and dries naturally.
2. a kind of titanium alloy high bond strength according to claim 1 electroplates brown lead oxide technique, it is characterised in that：It is described Anode active additive is gelatin.
CN201610992939.XA 2016-10-30 2016-10-30 High titanium alloy bonding strength lead dioxide electroplating process Pending CN106560530A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119296A (en) * 2017-06-27 2017-09-01 中国人民解放军第五七九工厂 A kind of method of anode activation titanium alloy electro-coppering
CN110791794A (en) * 2019-11-27 2020-02-14 云南电网有限责任公司电力科学研究院 Method and device for preparing converter valve thyristor by plating solution
CN113802159A (en) * 2021-09-15 2021-12-17 贵州天义电器有限责任公司 Surface treatment method for improving welding capacity of titanium alloy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1452276A (en) * 1972-12-06 1976-10-13 Secr Defence Electrolytically-produced lead dioxide battery plates
CN101407930A (en) * 2007-10-12 2009-04-15 中国船舶重工集团公司第七二五研究所 Titanium alloy high bond strength gold plating process
CN102534652A (en) * 2011-12-28 2012-07-04 南京理工大学 Preparation method for titanium base tin-doped lead dioxide electrode
CN104947162A (en) * 2015-07-22 2015-09-30 四川华丰企业集团有限公司 Titanium alloy surface electroplating method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1452276A (en) * 1972-12-06 1976-10-13 Secr Defence Electrolytically-produced lead dioxide battery plates
CN101407930A (en) * 2007-10-12 2009-04-15 中国船舶重工集团公司第七二五研究所 Titanium alloy high bond strength gold plating process
CN102534652A (en) * 2011-12-28 2012-07-04 南京理工大学 Preparation method for titanium base tin-doped lead dioxide electrode
CN104947162A (en) * 2015-07-22 2015-09-30 四川华丰企业集团有限公司 Titanium alloy surface electroplating method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姜妍妍 等: ""钛基二氧化铅电极的研究进展"", 《表面技术》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107119296A (en) * 2017-06-27 2017-09-01 中国人民解放军第五七九工厂 A kind of method of anode activation titanium alloy electro-coppering
CN110791794A (en) * 2019-11-27 2020-02-14 云南电网有限责任公司电力科学研究院 Method and device for preparing converter valve thyristor by plating solution
CN113802159A (en) * 2021-09-15 2021-12-17 贵州天义电器有限责任公司 Surface treatment method for improving welding capacity of titanium alloy

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Application publication date: 20170412