CN109972127A - A kind of preparation method of high anti-corrosion chemical Ni-plating layer - Google Patents

A kind of preparation method of high anti-corrosion chemical Ni-plating layer Download PDF

Info

Publication number
CN109972127A
CN109972127A CN201910361605.6A CN201910361605A CN109972127A CN 109972127 A CN109972127 A CN 109972127A CN 201910361605 A CN201910361605 A CN 201910361605A CN 109972127 A CN109972127 A CN 109972127A
Authority
CN
China
Prior art keywords
plating
chemical
nickel
layer
phosphorus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910361605.6A
Other languages
Chinese (zh)
Inventor
张德忠
赵涛
毛祖国
邓日智
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Material Protection Research Institute Co Ltd
Original Assignee
Wuhan Material Protection Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Material Protection Research Institute Co Ltd filed Critical Wuhan Material Protection Research Institute Co Ltd
Priority to CN201910361605.6A priority Critical patent/CN109972127A/en
Publication of CN109972127A publication Critical patent/CN109972127A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The present invention provides a kind of preparation method of high anti-corrosion chemical Ni-plating layer, and include the following steps: a. pre-treatment: substrate successively carries out chemical degreasing, electrolytic degreasing, acid pickling and rust removing, thoroughly removes surface and oil contaminant and rust staining；B. bottom chemical nickel plating (middle phosphorus): with the middle phosphorus chemistry nickel coating of the quick one layer of phosphorus content 6%~9% of plating of the plating speed not less than 12 μm/h, and according to base surface roughness determine in phosphorus chemistry nickel coating thickness, it is ensured that the coating is substantially non-porous；C. surface layer chemical nickel plating (high phosphorus): the high phosphorus chemical plating nickel layer of one layer of phosphorus content 9%~12% of plating again on middle phosphorus coating；D. it is heat-treated after plating.The present invention can not only greatly improve the corrosion resistance of chemical Ni-plating layer, but also can reduce thickness of coating 30-50 ℅ under the premise of keeping coating identical corrosion proof, and production efficiency improves 2 times, substantially reduces manufacturing cost.

Description

A kind of preparation method of high anti-corrosion chemical Ni-plating layer
Technical field
The invention belongs to metal and nonmetallic surface processing technology fields, and in particular to a kind of high anti-corrosion chemical Ni-plating layer Preparation method.
Background technique
Chemical nickel plating is a kind of important process for treating surface, has the spies such as coating is uniform, binding force is high, beautiful beauty Point can make material obtain excellent corrosion resistance, wearability, weldability, nonmetallic materials can also be made to metallize, therefore answer extensively For fields such as aerospace, petrochemical industry, automobile ship, telecommunications, medical facility, electromagnetic protections.
Chemical Ni-plating layer is cathodic electrodeposition coating, once there are the aperture of sensible base material or breakages on surface, nickel coating is just It can fast erosion.Therefore, the corrosion resisting property of chemical Ni-plating layer is largely dependent on porosity.But in coating growth course, A large amount of hydrogen gas bubbles are precipitated from surface, and coating inevitably forms small pin hole in the incipient stage.It is substantially non-porous to obtain Coating generally requires the coating that the plating on matrix is greater than 30 μm.For requiring high anti-corrosion (1000h of resistance to neutral salt spray or more) Use condition, chemical Ni-plating layer then require thickness to reach 50 μm or thicker.
The characteristics of chemical nickel plating is due to self-catalyzed reaction, nickel can also be deposited on cell wall and phase while depositing on workpiece It closes on pipeline, reduces the utilization rate of nickel；Meanwhile if the deposition on cell wall and pipeline is cleaned not in time, will cause coating it is coarse, The quality problems such as corrosion resistance is low.Therefore, coating bath and clean tank wall and pipeline are needed to frequently replace in chemical nickel plating production, causes to give birth to Low efficiency is produced, production maintenance is difficult.On the other hand, in chemical nickel plating reaction process, by-product phosphite, foreign ion and The K that plating, plating solution generate during adding+、Na+、NH4 +、SO4 2-Equal liquid can be accumulated, Yi Yinqi with the extension of service life Plating solution ageing failure, discarded plating solution of finally having to.It can be seen that wanting unitary system for 50 μm of chemical Ni-plating layers, plating time is needed 5-8h, bath temperature need to be maintained at 85 DEG C or more, and not only production efficiency is low, but also energy consumption is high, and plating solution consumption is big, thereby result in life It is high to produce cost.
Therefore, in view of the defect of 50 μm of production or more high anti-corrosion chemical Ni-plating layer technologies, there is an urgent need to develop gone out one kind both It is able to satisfy high corrosion-resistant requirement, and the preparation method of production efficiency, the chemical Ni-plating layer for reducing production cost can be improved.
Summary of the invention
In view of the problems of the existing technology, the technical solution that the present invention uses to solve problems of the prior art It is as follows:
A kind of preparation method of high anti-corrosion chemical Ni-plating layer, which comprises the steps of:
Step 1, pre-treatment: plating steel substrate is successively subjected to chemical degreasing, electrolytic degreasing, acid pickling and rust removing, is thoroughly removed Surface and oil contaminant and rust staining are removed, is then rinsed with tap water, is finally rinsed well with deionized water；
Step 2, bottom chemical nickel plating (middle phosphorus): will premenstrual treated plating in phosphorus chemistry nickel plating solution during substrate immerses The middle phosphorus chemistry nickel coating of one layer of phosphorus content 6%~9%, and according to the thickness of phosphorus chemistry nickel coating in base surface roughness determination It spends (being usually no more than 25 μm), it is ensured that the coating gap is less；
Middle phosphorus chemistry nickel plating solution includes each component of following concentration: nickel sulfate 18-28g/L, hypophosphorous acid in the step 2 Sodium 20-30g/L, lactic acid 25-35g/L, malic acid 5-10g/L, promotor 2-5g/L, thiocarbamide 1-3mg/L.
The plating conditions of the step 2 are pH=4.5-5.0,80-95 DEG C of temperature, after the completion of plating, not washed, immediately Into the next step.
Step 3, surface layer chemical nickel plating (high phosphorus): after step 2 processing, workpiece is immersed to high phosphorus chemistry as quickly as possible The high phosphorus chemical plating nickel layer of one layer of phosphorus content 9%~12% of plating again in nickel plating solution controls thickness of coating at 8-20 μm；
High phosphorus chemical plating nickel solution includes each component of following concentration: nickel sulfate 20-35g/L, hypophosphorous acid in the step 3 Sodium 22-40g/L, malic acid 15-25g/L, citric acid 15-25g/L, succinic acid 5-12g/L, thiocarbamide 1-3mg/L.
The plating item of the step 3 is pH=4.6-5.5,80-95 DEG C of temperature, after plating is complete, is cleaned with deionized water dry Only, hot blast drying is used.
It is heat-treated after step 4, plating: the workpiece for being coated with chemical Ni-plating layer being subjected to dehydrogenation: keeping 2h at 200 DEG C.
Preferably, the chemical degreasing technique in the step 1 are as follows: 20-40g/L sodium hydroxide, 30-45g/L sodium carbonate, 25-40g/L sodium metasilicate, 1-2mL/LOP-10, treatment temperature is 45 DEG C~70 DEG C, soaking time 3-10min, to remove test piece table Face greasy dirt and grease after taking-up, are rinsed well with tap water.
Preferably, the electrolytic degreasing technique in the step 1 are as follows: 40-80g/L sodium hydroxide, 20-40g/L sodium metasilicate are low Foam surfactants are a small amount of, and temperature is controlled at 45 DEG C~65 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electricity 30s is solved, steel surface residual grease and pollutant are thoroughly removed, power-off is taken out test piece, rinsed with tap water.
Preferably, the Acid Rust Removalling Technics in the step 1 are as follows: 150-400mL/L HCl (commercial quality score 36-38 The concentrated hydrochloric acid of ℅), 1g/L hexamethylenetetramine impregnates 3~5min at room temperature.After taking-up, rinsed well with tap water.
Preferably, the middle phosphorus chemistry nickel plating technology in the step 2 are as follows: nickel sulfate 20-24g/L, sodium hypophosphite 22-6g/ L, lactic acid 25-30g/L, malic acid 6-8g/L, promotor 3-5g/L, thiocarbamide 1-3mg/L, pH=4.5-4.8,86-90 DEG C of temperature, Plating speed is kept to be not less than 12 μm/h.
Preferably, plating thickness is determined according to base surface roughness in the step 2: base surface roughness Ra= At 0.5-1.5 μm, 5-8 μm of plating；At Ra=1.5-5.0 μm, 8-12 μm of plating；At Ra=5.0-10.0 μm, plating 12-15 μ m；At 10.0 μm of Ra >, 15-25 μm of plating.
Preferably, the high phosphorus chemical plating technique in the step 3 are as follows: nickel sulfate 25-30g/L, sodium hypophosphite 28-35g/L, Malic acid 20-25g/L, citric acid 15-20g/L, succinic acid 8-12g/L, thiocarbamide 1-3mg/L, pH=4.8-5.2, temperature 86-90 DEG C, keep plating speed to be not higher than 12 μm/h, to obtain the high-densit coating of low porosity.
Step 2, step 3 are not limited only to successively carry out plating twice, can also be appointed by step 2, one or two kinds of formed of step 3 Meaning combination, to obtain two layers or two layers of combination of the above coating.
The present invention has the advantage that
1. under the premise of guaranteeing identical corrosion proof, total thickness of coating can be greatly reduced compared with single coating, reduce Plating solution consumption, to substantially reduce production cost.
2. plating time also accordingly shortens, and therefore, production efficiency greatly improves since required overall thickness reduces.
3. combined plating can obtain corrosion resisting property more preferably chemical Ni-plating layer than single coating.
Specific embodiment
Below by embodiment, the technical solutions of the present invention will be further described:
Embodiment 1
Substrate is Q235 steel, and base surface roughness is Ra=0.5-1.5 μm.
Step 1, pre-treatment:
Chemical degreasing, electrolytic degreasing, acid pickling and rust removing are successively carried out to plating steel substrate, thoroughly removes surface and oil contaminant and rust Then spot is rinsed with tap water, finally rinsed well with deionized water.
Step 2, bottom chemical nickel plating (middle phosphorus):
Substrate is immersed to the middle phosphorus chemistry nickel coating of one layer of phosphorus content 6%~9% of plating in chemical plating fluid, and according to substrate The thickness (being usually no more than 25 μm) of phosphorus chemistry nickel coating during surface roughness is determining, it is ensured that the coating is substantially non-porous.
Plating solution: nickel sulfate 24g/L, sodium hypophosphite 26g/L, lactic acid 25g/L, malic acid 8g/L, promotor 5g/L, thiocarbamide 2mg/L。
Plating conditions are pH=4.6,88 DEG C of temperature, after plating 1h, not wash, immediately enter the next step.
Step 3, surface layer chemical nickel plating (high phosphorus):
After step 2 processing, workpiece is immersed as quickly as possible in following solutions again one layer of phosphorus content 9% of plating~ 12% high phosphorus chemical plating nickel layer.
Plating solution: nickel sulfate 28g/L, sodium hypophosphite 30g/L, malic acid 25g/L, citric acid 20g/L, succinic acid 8g/L, sulphur Urea 3mg/L.
Plating conditions: pH=4.8,90 DEG C of temperature, plating 2.5h is cleaned up with deionized water, uses hot blast drying.
It is heat-treated after step 4, plating:
The workpiece for being coated with chemical Ni-plating layer is subjected to dehydrogenation: keeping 2h at 200 DEG C.
Wherein:
Chemical degreasing technique in step 1 are as follows: 40g/L sodium hydroxide, 340g/L sodium carbonate, 25g/L sodium metasilicate, 1mL/ LOP-10, treatment temperature is 55 DEG C~60 DEG C, soaking time 5min, to remove strip greasy dirt and grease.After taking-up, with certainly Water is rinsed well.
Electrolytic degreasing technique in step 1 are as follows: 60g/L sodium hydroxide, 30g/L sodium metasilicate, low foaming surfactant is a small amount of, Temperature control thoroughly removes steel at 60 DEG C~65 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s Remained on surface grease and pollutant.Test piece is taken out in power-off, is rinsed with tap water.
Acid Rust Removalling Technics in step 1 are as follows: 300mL/L hydrochloric acid (commercial quality score >=31 ℅), six methine of 1g/L Tetramine impregnates 4min at room temperature, after taking-up, is rinsed well with tap water.
After tested, through above step preparation ni-p alloy coating overall thickness be 37 μm, neutral salt spray test 720h, be by Step 2 technique prepares 2.6 times of the neutral salt spray test time of the single ni-p alloy coating of same thickness, is identical by step 3 1.8 times of the neutral salt spray test time of the single ni-p alloy coating of the same thickness of technique preparation.
Embodiment 2
Substrate is Q345 steel, and base surface roughness is Ra=3.5 μm.
Step 1, pre-treatment:
Chemical degreasing, electrolytic degreasing, acid pickling and rust removing are successively carried out to plating steel substrate, thoroughly removes surface and oil contaminant and rust Then spot is rinsed with tap water, finally rinsed well with deionized water.
Step 2, bottom chemical nickel plating (middle phosphorus):
Substrate is immersed to the middle phosphorus chemistry nickel coating of one layer of phosphorus content 6%~9% of plating in chemical plating fluid, and according to substrate The thickness (being usually no more than 25 μm) of phosphorus chemistry nickel coating during surface roughness is determining, it is ensured that the coating is substantially non-porous.
Plating solution: nickel sulfate 24g/L, sodium hypophosphite 22g/L, lactic acid 25g/L, malic acid 7g/L, promotor 5g/L, thiocarbamide 2mg/L。
Plating conditions are pH=4.6-4.8,90 DEG C of temperature, after plating 2.0h, not wash, immediately enter next step work Sequence.
Step 3, surface layer chemical nickel plating (high phosphorus):
After step 2 processing, workpiece is immersed as quickly as possible in following solutions again one layer of phosphorus content 9% of plating~ 12% high phosphorus chemical plating nickel layer controls thickness of coating at 8-20 μm.
Plating solution: nickel sulfate 25g/L, sodium hypophosphite 32g/L, malic acid 20g/L, citric acid 19g/L, succinic acid 10g/L, sulphur Urea 1.5mg/L.
Plating conditions: pH=4.8-5.0, temperature (88 ± 2) DEG C after plating 1h, are cleaned up with deionized water, use hot wind Drying.
It is heat-treated after step 4, plating:
The workpiece for being coated with chemical Ni-plating layer is subjected to dehydrogenation: keeping 2h at 200 DEG C.
Wherein: the chemical degreasing technique in step 1 are as follows: 27g/L sodium hydroxide, 40g/L sodium carbonate, 40g/L sodium metasilicate, 2mL/LOP-10, treatment temperature is 50 DEG C~55 DEG C, soaking time 8min, to remove strip greasy dirt and grease.After taking-up, It is rinsed well with tap water.
Electrolytic degreasing technique in step 1 are as follows: 80g/L sodium hydroxide, 20g/L sodium metasilicate, low foaming surfactant is a small amount of, Temperature control thoroughly removes steel at 55 DEG C~60 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s Remained on surface grease and pollutant.Test piece is taken out in power-off, is rinsed with tap water.
Acid Rust Removalling Technics in step 1 are as follows: 280mL/L hydrochloric acid (commercial quality score >=31 ℅), six methine of 1g/L Tetramine impregnates 3~5min at room temperature, after taking-up, is rinsed well with tap water.
After tested, overall thickness is 28 μm to the nickel-phosphorus alloy through above step preparation layer by layer, and neutral salt spray test 600h is It is by step 3 phase by 2.1 times of the neutral salt spray test time of the single ni-p alloy coating of step 2 technique preparation same thickness With 1.5 times of the neutral salt spray test time of the single ni-p alloy coating of the same thickness of technique preparation.
Embodiment 3
Substrate is Q235 steel, and base surface roughness is Ra=5.0 μm.
Step 1, pre-treatment:
Chemical degreasing, electrolytic degreasing, acid pickling and rust removing are successively carried out to plating steel substrate, thoroughly removes surface and oil contaminant and rust Then spot is rinsed with tap water, finally rinsed well with deionized water.
Step 2, bottom chemical nickel plating (middle phosphorus):
Substrate is immersed to the middle phosphorus chemistry nickel coating of one layer of phosphorus content 6%~9% of plating in chemical plating fluid, and according to substrate The thickness (being usually no more than 25 μm) of phosphorus chemistry nickel coating during surface roughness is determining, it is ensured that the coating is substantially non-porous.
Plating solution: nickel sulfate 20g/L, sodium hypophosphite 25g/L, lactic acid 25g/L, malic acid 8g/L, promotor 5g/L, thiocarbamide 1mg/L。
Plating conditions are pH=4.5-4.6,88 DEG C -90 DEG C of temperature, plating speed are kept to be not less than 12 μm/h, after plating 1.5h, It not wash, immediately enter the next step.
Step 3, surface layer chemical nickel plating (middle phosphorus):
After step 2 processing, workpiece is immersed to plating in the plating solution of step 2 same solution composition as quickly as possible.
Plating conditions after plating 1.5h, are cleaned up with deionized water, use hot blast drying with step 2.
It is heat-treated after step 4, plating:
The workpiece for being coated with chemical Ni-plating layer is subjected to dehydrogenation: keeping 2h at 200 DEG C.
Chemical degreasing technique in step 1 are as follows: 20-40g/L sodium hydroxide, 30-45g/L sodium carbonate, 25-40g/L silicic acid Sodium, 1-2mL/L OP-10, treatment temperature is 45 DEG C~70 DEG C, soaking time 3-10min, to remove strip greasy dirt and oil Rouge after taking-up, is rinsed well with tap water.
Electrolytic degreasing technique in step 1 are as follows: 40-80g/L sodium hydroxide, 20-40g/L sodium metasilicate, low bubble surface-active Agent is a small amount of, and temperature is controlled at 45 DEG C~65 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s, thoroughly Remove steel surface residual grease and pollutant.Test piece is taken out in power-off, is rinsed with tap water.
Acid Rust Removalling Technics in step 1 are as follows: 150-400mL/L hydrochloric acid (concentrated hydrochloric acid of commercial quality score 36-38 ℅), 1g/L hexamethylenetetramine impregnates 3~5min at room temperature, after taking-up, is rinsed well with tap water.
After tested, overall thickness is 30 μm to the nickel-phosphorus alloy through above step preparation layer by layer, and neutral salt spray test 576h is By 1.9 times of the neutral salt spray test time of the single ni-p alloy coating of the continuous plating preparation same thickness of step 2 technique.
Embodiment 4
Substrate is Q235 steel, and base surface roughness is Ra=0.5-1.5 μm.
Step 1, pre-treatment:
Chemical degreasing, electrolytic degreasing, acid pickling and rust removing are successively carried out to plating steel substrate, thoroughly removes surface and oil contaminant and rust Then spot is rinsed with tap water, finally rinsed well with deionized water.
Step 2, bottom chemical nickel plating (middle phosphorus):
Substrate is immersed into pH=4.5-5.0, one layer of phosphorus content 6%~9% of plating in 80-95 DEG C of temperature of chemical plating fluid Middle phosphorus chemistry nickel coating, and according to base surface roughness determine in phosphorus chemistry nickel coating thickness (being usually no more than 25 μm), Ensure that the coating is substantially non-porous.
Plating solution: nickel sulfate 20g/L, sodium hypophosphite 25g/L, lactic acid 25g/L, malic acid 7g/L, promotor 3.5g/L, thiocarbamide 2mg/L。
Plating conditions are pH=4.8-5.0,90 DEG C -92 DEG C of temperature, plating speed are kept to be not less than 12 μm/h, after plating 1h, no It washes, immediately enters the next step.
Step 3, surface layer chemical nickel plating (middle phosphorus):
After step 2 processing, workpiece is immersed to plating in the plating solution of step 2 same solution composition as quickly as possible.
Plating conditions after plating 1h, are cleaned up with deionized water, use hot blast drying with step 2.
Step 4, surface layer chemical nickel plating (high phosphorus):
After step 3 processing, workpiece is immersed as quickly as possible in following solutions again one layer of phosphorus content 9% of plating~ 12% high phosphorus chemical plating nickel layer controls thickness of coating at 8-20 μm.
Plating solution: nickel sulfate 28g/L, sodium hypophosphite 230g/L, malic acid 22g/L, citric acid 18g/L, succinic acid 10g/L, Thiocarbamide 1mg/L.
Plating conditions: pH=4.8-5.0, after plating 1h, is cleaned up with deionized water, uses hot wind by 86 DEG C -88 DEG C of temperature Drying.
It is heat-treated after step 5, plating:
The workpiece for being coated with chemical Ni-plating layer is subjected to dehydrogenation: keeping 2h at 200 DEG C.
Wherein: the chemical degreasing technique in step 1 are as follows: 35g/L sodium hydroxide, 40g/L sodium carbonate, 28g/L sodium metasilicate, 1mL/LOP-10, treatment temperature is 45 DEG C~50 DEG C, soaking time 10min, to remove strip greasy dirt and grease.It takes out Afterwards, it is rinsed well with tap water.
Electrolytic degreasing technique in step 1 are as follows: 60g/L sodium hydroxide, 30g/L sodium metasilicate, low foaming surfactant is a small amount of, Temperature control thoroughly removes steel at 55 DEG C~60 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s Remained on surface grease and pollutant.Test piece is taken out in power-off, is rinsed with tap water.
Acid Rust Removalling Technics in step 1 are as follows: 200mL/L hydrochloric acid (concentrated hydrochloric acid of 33 ℅ of commercial quality score), 1g/L six Methine tetramine, impregnates 5min at room temperature.After taking-up, rinsed well with tap water.
After tested, overall thickness is 30 μm to the nickel-phosphorus alloy through above step preparation layer by layer, and neutral salt spray test 840h is It is by step 3 phase by 2.9 times of the neutral salt spray test time of the single ni-p alloy coating of step 2 technique preparation same thickness With 2.0 times of the neutral salt spray test time of the single ni-p alloy coating of the same thickness of technique preparation.
Embodiment 5
Substrate is Q345 steel, and base surface roughness is Ra=3.5-5.5 μm.
Step 1, pre-treatment
Chemical degreasing, electrolytic degreasing, acid pickling and rust removing are successively carried out to plating steel substrate, thoroughly removes surface and oil contaminant and rust Then spot is rinsed with tap water, finally rinsed well with deionized water.
Step 2, bottom chemical nickel plating (high phosphorus)
Substrate is immersed to the high phosphorus chemical plating nickel layer of one layer of phosphorus content 9%~12% of plating again in following solutions.
Plating solution: nickel sulfate 28g/L, sodium hypophosphite 30g/L, malic acid 25g/L, citric acid 20g/L, succinic acid 8g/L, sulphur Urea 3mg/L.
Plating conditions: pH=4.8, after plating 1h, not wash, immediately enter the next step by 90 DEG C of temperature.
Step 3, surface layer chemical nickel plating (high phosphorus)
After step 2 processing, workpiece is immersed as quickly as possible in following solutions again one layer of phosphorus content 9% of plating~ 12% high phosphorus chemical plating nickel layer.
Plating solution: nickel sulfate 28g/L, sodium hypophosphite 30g/L, malic acid 25g/L, citric acid 20g/L, succinic acid 8g/L, sulphur Urea 3mg/L.
Plating conditions: pH=4.8,90 DEG C of temperature, plating 1.5h is cleaned up with deionized water, uses hot blast drying.
It is heat-treated after step 4, plating:
The workpiece for being coated with chemical Ni-plating layer is subjected to dehydrogenation: keeping 2h at 200 DEG C.
Chemical degreasing technique in step 1 are as follows: 30g/L sodium hydroxide, 37.5g/L sodium carbonate, 36g/L sodium metasilicate, 1.5mL/LOP-10, treatment temperature is 45 DEG C~50 DEG C, soaking time 3min, to remove strip greasy dirt and grease, is taken out Afterwards, it is rinsed well with tap water.
Electrolytic degreasing technique in step 1 are as follows: 70g/L sodium hydroxide, 25g/L sodium metasilicate, low foaming surfactant is a small amount of, Temperature control thoroughly removes steel at 60 DEG C~65 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s Remained on surface grease and pollutant, power-off are taken out test piece, are rinsed with tap water.
Acid Rust Removalling Technics in step 1 are as follows: 380mL/L hydrochloric acid (concentrated hydrochloric acid of 31 ℅ of commercial quality score), 1g/L six Methine tetramine, impregnates 3min at room temperature.After taking-up, rinsed well with tap water.
After tested, through above step preparation ni-p alloy coating overall thickness be 24 μm, neutral salt spray test 768h, be by Step 3 technique prepares 1.8 times of the neutral salt spray test time of the single ni-p alloy coating of same thickness.
Protection scope of the present invention is not limited to the above embodiments, it is clear that those skilled in the art can be to this hair It is bright to carry out various changes and deformation without departing from scope and spirit of the present invention.If these changes and deformation belong to power of the present invention In the range of benefit requirement and its equivalent technologies, then including the intent of the present invention also includes these changes and deforms.

Claims (9)

1. a kind of preparation method of high anti-corrosion chemical Ni-plating layer, which comprises the steps of:
Step 1, pre-treatment: plating steel substrate is successively subjected to chemical degreasing, electrolytic degreasing, acid pickling and rust removing, thoroughly removes table Face greasy dirt and rust staining, are then rinsed with tap water, are finally rinsed well with deionized water；
Step 2, bottom chemical nickel plating: will premenstrual treated during substrate immerses in phosphorus chemistry nickel plating solution one layer of phosphorus content of plating 6%~9% middle phosphorus chemistry nickel coating, and according to the thickness of phosphorus chemistry nickel coating in base surface roughness determination, it is ensured that it should Coating gap is less；
Step 3, surface layer chemical nickel plating: after step 2 processing, workpiece is immersed as quickly as possible in high phosphorus chemical plating nickel solution The high phosphorus chemical plating nickel layer of one layer of phosphorus content 9%~12% of plating again controls thickness of coating at 8-20 μm；
It is heat-treated after step 4, plating: the workpiece for being coated with chemical Ni-plating layer being subjected to dehydrogenation: keeping 2h at 200 DEG C.
2. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 2 Middle phosphorus chemistry nickel plating solution includes each component of following concentration: nickel sulfate 18-28g/L, sodium hypophosphite 20-30g/L, lactic acid 25- 35g/L, malic acid 5-10g/L, promotor 2-5g/L, thiocarbamide 1-3mg/L；
The plating conditions of the step 2 are pH=4.5-5.0,80-95 DEG C of temperature, after the completion of plating, not wash, immediately enter The next step.
3. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 3 High phosphorus chemical plating nickel solution includes each component of following concentration: nickel sulfate 20-35g/L, sodium hypophosphite 22-40g/L, malic acid 15-25g/L, citric acid 15-25g/L, succinic acid 5-12g/L, thiocarbamide 1-3mg/L；
The plating item of the step 3 is pH=4.6-5.5,80-95 DEG C of temperature, after plating is complete, is cleaned up with deionized water, is used Hot blast drying.
4. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 1 Chemical degreasing technique are as follows: 20-40g/L sodium hydroxide, 30-45g/L sodium carbonate, 25-40g/L sodium metasilicate, 1-2mL/LOP-10, Treatment temperature is 45 DEG C~70 DEG C, and soaking time 3-10min after taking-up, uses tap water to remove strip greasy dirt and grease It rinses well.
5. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 1 Electrolytic degreasing technique are as follows: 40-80g/L sodium hydroxide, 20-40g/L sodium metasilicate, low foaming surfactant is a small amount of, temperature control At 45 DEG C~65 DEG C, first anode electrolysis 90s, then catholyte 30s, then anode electrolysis 30s, steel surface residual is thoroughly removed Grease and pollutant, power-off are taken out test piece, are rinsed with tap water.
6. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 1 Acid Rust Removalling Technics are as follows: 150-400mL/L HCl (concentrated hydrochloric acid of commercial quality score 36-38 ℅), six methine four of 1g/L Amine impregnates 3~5min at room temperature, after taking-up, is rinsed well with tap water.
7. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 2 Middle phosphorus chemistry nickel plating technology are as follows: nickel sulfate 20-24g/L, sodium hypophosphite 22-6g/L, lactic acid 25-30g/L, malic acid 6-8g/ L, promotor 3-5g/L, thiocarbamide 1-3mg/L, pH=4.5-4.8, keep plating speed to be not less than 12 μm/h by 86-90 DEG C of temperature.
8. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 2 Plating thickness is determined according to base surface roughness: base surface roughness Ra=0.5-1.5 μm when, 5-8 μm of plating；Ra= At 1.5-5.0 μm, 8-12 μm of plating；At Ra=5.0-10.0 μm, 12-15 μm of plating；At 10.0 μm of Ra >, 15-25 μm of plating.
9. a kind of preparation method of high anti-corrosion chemical Ni-plating layer as described in claim 1, it is characterised in that: in the step 3 High phosphorus chemical plating technique are as follows: nickel sulfate 25-30g/L, sodium hypophosphite 28-35g/L, malic acid 20-25g/L, citric acid 15- 20g/L, succinic acid 8-12g/L, thiocarbamide 1-3mg/L, pH=4.8-5.2, keep plating speed to be not higher than 12 μm/h by 86-90 DEG C of temperature, To obtain the high-densit coating of low porosity.
CN201910361605.6A 2019-04-30 2019-04-30 A kind of preparation method of high anti-corrosion chemical Ni-plating layer Pending CN109972127A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910361605.6A CN109972127A (en) 2019-04-30 2019-04-30 A kind of preparation method of high anti-corrosion chemical Ni-plating layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910361605.6A CN109972127A (en) 2019-04-30 2019-04-30 A kind of preparation method of high anti-corrosion chemical Ni-plating layer

Publications (1)

Publication Number Publication Date
CN109972127A true CN109972127A (en) 2019-07-05

Family

ID=67087337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910361605.6A Pending CN109972127A (en) 2019-04-30 2019-04-30 A kind of preparation method of high anti-corrosion chemical Ni-plating layer

Country Status (1)

Country Link
CN (1) CN109972127A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110453205A (en) * 2019-07-30 2019-11-15 杨小荣 A kind of nickel chemical plating technology of aluminum foil material circuit board
CN111962117A (en) * 2020-07-06 2020-11-20 青岛凯瑞电子有限公司 Multilayer nickel plating process for ceramic-metal shell
CN112626571A (en) * 2020-11-25 2021-04-09 成都宏明双新科技股份有限公司 Mixed nickel plating method for improving salt spray resistance test performance
CN115821236A (en) * 2022-12-15 2023-03-21 江苏东方九天新能源材料有限公司 Nickel-cobalt-plated steel belt for lithium battery shell and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018905A (en) * 2015-07-28 2015-11-04 太原理工大学 Preparation method for chemically plating nickel-phosphorus coating on surface of anchor rod steel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105018905A (en) * 2015-07-28 2015-11-04 太原理工大学 Preparation method for chemically plating nickel-phosphorus coating on surface of anchor rod steel

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
张剑波等: "《清洁技术基础教程》", 31 July 2004, 中国环境科学出版社 *
徐湘缃: "《实用防腐蚀工程施工手册》", 30 April 2000, 化学工业出版社 *
赵丹等: "《低碳钢表面化学复合镀工艺和性能研究》", 31 July 2017, 冶金工业出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110453205A (en) * 2019-07-30 2019-11-15 杨小荣 A kind of nickel chemical plating technology of aluminum foil material circuit board
CN110453205B (en) * 2019-07-30 2024-01-12 珠海市兴铝电子科技有限公司 Chemical nickel plating process for aluminum foil material circuit board
CN111962117A (en) * 2020-07-06 2020-11-20 青岛凯瑞电子有限公司 Multilayer nickel plating process for ceramic-metal shell
CN111962117B (en) * 2020-07-06 2021-11-23 青岛凯瑞电子有限公司 Multilayer nickel plating process for ceramic-metal shell
CN112626571A (en) * 2020-11-25 2021-04-09 成都宏明双新科技股份有限公司 Mixed nickel plating method for improving salt spray resistance test performance
CN115821236A (en) * 2022-12-15 2023-03-21 江苏东方九天新能源材料有限公司 Nickel-cobalt-plated steel belt for lithium battery shell and preparation method thereof
CN115821236B (en) * 2022-12-15 2023-12-12 江苏东方九天新能源材料有限公司 Nickel-cobalt plated steel strip for lithium battery shell and preparation method thereof

Similar Documents

Publication Publication Date Title
CN109972127A (en) A kind of preparation method of high anti-corrosion chemical Ni-plating layer
CN107779713B (en) A kind of beryllium alumin(i)um alloy and preparation method thereof
CN105177640A (en) Efficient high-performance and high-hardness chromium plating process
CN101705508A (en) Plating liquid for plating micro-crack nickel and use thereof
CN111058068A (en) Processing technology of zinc-plated nickel alloy
CN108315788A (en) A kind of stainless steel continuous electroplating nickel phosphorus boron alloy roll bending and preparation method thereof
CN102605358A (en) Application of chemical plating nickel phosphorus alloy to triallyl cyanurate (TAC) film production line
CN106119907A (en) A kind of chrome-plating method of automobile rustless steel tail gas decoration
CN107574430A (en) A kind of silicate bright blue passivation liquid and preparation method thereof
CN103806061A (en) Process for reducing low internal stress of hub electroplated layer through semi-bright nickel electroplating procedure
CN107190287A (en) A kind of plating solution and its electro-plating method for electroplating pearl nickel on stainless steel
CN106011895A (en) Cleaning agent for electrogalvanizing pretreatment
CN109440039A (en) A kind of production technology of galvanized wire
CA1143632A (en) Method and means for treatment of surfaces
CN109402685B (en) Process for improving thickness of zinc-nickel plated low-zone coating
CN109023336A (en) A kind of environment-friendly type rare-earth salts color passivation solution and preparation method thereof
CN105970198A (en) Method for preparing multicomponent alloy clad layer spherical cap for support
CN112553612B (en) Synchronous pickling and passivating method for stainless steel parts
JPH0759755B2 (en) Method for manufacturing A-l alloy coated plate for automobiles having excellent system rust resistance
CN102400119A (en) Chemical nickel plating method on magnesium alloy
CN108754475A (en) A kind of environment-friendly type blue and white passivation solution and preparation method thereof
KR20010067721A (en) Method process for forming copper and nickel-plated of electrolytic plating in magnesium compound
KR100528638B1 (en) Plating Process of Nickel on Magnesium Alloy
CN117845309A (en) Corrosion-resistant composite coating based on corrosion intensity self-adaption and preparation method thereof
CN107904633A (en) A kind of zinc alloy surface processing method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190705