CN107313088B - A method of based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition - Google Patents
A method of based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- 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
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- 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
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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- 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
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
The invention discloses a kind of methods based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition, the method includes successively being mechanically polished to metal base surface, heat alkali liquid degreasing, anodic oxidation, Pd2+‑Sn2+Sensitization activation, Ni-P chemical plating and the nanocrystalline functional coating of pulse electrodeposition.The method of the invention is conducive to a variety of coating of subsequent electrodeposition using chemical Ni-P plating film as transition zone, such as: Ni, Cu, and amorphous institutional framework helps to refine the crystallite dimension of subsequent plating layer；The ageing treatment of low temperature in the method is conducive to the growth stress for alleviating Ni-P film, avoids the tendency of cracking；The surface that the method for the invention is suitable for a variety of active metals such as pure titanium, aluminium or magnesium is modified；Carry out the big thickness nanocrystalline deposit of electro-deposition using chemical Ni-P plating film as transition zone, it is good using scratching instrument and the method validation of cross-section observation interface binding power, can be used for general low load it is wear-resistant under the conditions of engineering surface material.
Description
Technical field
The invention belongs to metal material fields, and the surface for being related to metal material is modified, specially a kind of to be based on anodic oxidation
The method of the nanocrystalline functional coating of porous metals primary surface electro-deposition.
Background technique
Due to having many advantages, such as that high specific strength, excellent corrosion-proof performance and thermal stability are high, pure titanium and its alloy are by widely
It is applied to the fields such as aerospace, 3D printing material, biomedicine.However, during actual use titanium alloy surface it is wear-resisting
The performances such as property, solderability are poor, thus seriously limit its application range.
To further increase pure titanium and its Alloyapplication range, it is bound to be modified its surface enhancing.Common surface
Modification technology mainly has: mechanical alloying, laser surface coating, agitating friction weldering, plasma two-lime piles, physical chemistry gas phase
Deposition etc..But current technology bottleneck is: titanium chemical activity is big, even if being exposed by after the pretreatment of the acid solutions such as HF acid
Come fresh Ti can spontaneously with the O in air2Reaction, promotes its surface passivation at one layer of fine and close oxidation film, is difficult at it
Surface grows functional coating, and leads to due to the presence of the oxidation film interface binding power between Titanium base and surface covering very
Seldom to guarantee.
It is modified in consideration of it, the simple and easy method of one kind need to be sought and carry out surface to titanium, the purpose is to keep titanium
The interface binding power of function of surface coating and Titanium base is improved while metal surface activity.
Summary of the invention
The technical issues of solution: it in order to overcome the drawbacks of the prior art, obtains a kind of while keeping Metal Substrate surface-active
And its interface binding power of function of surface coating and matrix, the present invention are suitble to porous by the method preparation aperture of anodic oxidation
Then metallic matrix uses Pd on its surface2+-Sn2+Sensitization is activated to restore Pd atom, and then carries out Ni-Pization
Plating is learned, makees institutional framework preparation for the nanocrystalline functional coating of subsequent electrodeposition.
Technical solution: a method of based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition, institute
State method include successively metal base surface is mechanically polished, heat alkali liquid degreasing, anodic oxidation, Pd2+-Sn2+Sensitization is lived
Change, Ni-P chemical plating and the nanocrystalline functional coating of pulse electrodeposition.
Preferably, specific step is as follows for the method:
Step 1, mechanical polishing: first roughly grinding metallic matrix using SiC waterproof abrasive paper, then uses Al2O3Antiscuffing paste into
Row polishing, until metallography microscope sem observation surface no marking；
Step 2, heat alkali liquid degreasing: the metallic matrix after mechanical polishing is placed in ultrasonic generator, and heat alkali liquid is added,
Treatment temperature is 65~80 DEG C, is sufficiently washed with deionized water after oscillation, drying for standby；
Step 3, anodic oxidation: in H2SO4In the solution of system, metal base surface, electricity are handled using D.C. regulated power supply
Press 100~120V, 5~8min of time, 30 DEG C of solution temperature, current density 0.2A/dm2~0.4A/dm2；
Step 4, Pd2+-Sn2+Sensitization activation: porous metal matrix made from step 3 is placed in drying in drying box, successively
It is sensitized, is activated, treatment temperature is 45 ± 5 DEG C, and the time is 3~5min；
Step 5, Ni-P chemical plating: by step 4, treated that metallic matrix is placed in chemical plating solution, pH be 9~10,
Under the conditions of temperature is 35 DEG C, the Pd atom obtained using sensitization activating and reducing is catalyzed in metal base surface generates active site, raw
Long Ni-P film；
The nanocrystalline functional coating of step 6, pulse electrodeposition: using the Ni-P film of step 5 generation as transition zone, and will be golden
Belong to matrix to be placed in electrolyte, electrolysis temperature is 30 DEG C, pH value 3~4, double-pulse parameters are as follows: 0.8~1.2A/ of current density
dm2, pulse frequency 1500Hz, make-to-break ratio 3:1 adjust electroplating time according to thickness of coating demand.
Preferably, the metallic matrix is pure titanium, aluminium or magnesium.
Preferably, the nanocrystalline functional coating is Ni, Cu or its nanocomposite coating.
Preferably, aging anneal processing is carried out before the nanocrystalline functional coating of pulse electrodeposition, the treatment temperature is
400 ± 25 DEG C, the time is 1.5~2h, air-cooled.
Preferably, the specification of the SiC waterproof abrasive paper is 800#、1200#Or 1500#；The Al2O3Partial size be 5nm.
Further, the composition of the heat alkali liquid are as follows: 15wt.%NaOH, 20wt.%Na2CO3, the surface 0.1g/L OP-10
Activating agent, remaining is deionized water.
Further, H in step 32SO4The component of system are as follows: 375g/L H2SO4, 62.5g/L HCl, 3~5g/L H2O2
Additive.
Further, sensitizing solution component in step 4: 30g/L SnCl2, 40g/L HCl, remaining is deionized water；Activation
Liquid component are as follows: 0.4g/L PdCl2, 15g/L HCl, remaining is deionized water.
Further, in step 5 chemical plating solution component are as follows: 20g/L NiSO4·H2O, 23g/L NaH2PO4·H2O,
11.7g/L Na3C6H2O3·H2O, 30g/L NH4Cl。
The principle of the method for the invention is: use anodizing technology, the prefabricated aperture of titanium-based surface 150~
300nm nano-pore, this hole, which plays the role of beating, pricks absorption and raising interface binding power；Then pre- in containing Sn-Pd sensitization activating solution
First forming core, the Pd restored plate Ni-P for subsequent chemistry and provide heterogeneous nucleation point, promote Ni-P alloy continued propagation；Meanwhile it adopting
With dipulse electro-deposition techniques, using chemical Ni-P plating as transition zone, in titanium-based surface deposition growth nanometer crystalline Ni functional coating.
The utility model has the advantages that (1) the method for the invention is conducive to subsequent electrodeposition using chemical Ni-P plating film as transition zone
A variety of coating, such as: Ni, Cu, and amorphous institutional framework helps to refine the crystallite dimension of subsequent plating layer；(2) the method
The ageing treatment of middle low temperature is conducive to the growth stress for alleviating Ni-P film, avoids the tendency of cracking；(3) of the present invention
The surface that method is suitable for a variety of active metals such as pure titanium, aluminium or magnesium is modified；(4) using chemical Ni-P plating film as transition zone
Electro-deposition big thickness nanocrystalline deposit, it is good using scratching instrument and the method validation of cross-section observation interface binding power, it can be used for
Engineering surface material under the conditions of general low load is wear-resistant.
Detailed description of the invention
Fig. 1 be the pure Titanium base of TA2 (left side), anode oxide film (in) and chemical Ni-P plating film (right side) optical picture in kind；
Fig. 2 is Ni―Ti anode oxidation rear surface porous character FE-SEM shape appearance figure and pore size statistical chart；
Wherein (a) is that Ni―Ti anode aoxidizes rear surface porous character FE-SEM shape appearance figure；It (b) is the partial enlarged view of (a)；
It (c) is pore size statistical chart；
Fig. 3 is the specimen surface FE-SEM pattern after anodic oxidation (a), sensitization-activation (b), chemical Ni-P plating film (c)
Figure；
Fig. 4 is anodic oxidation POROUS TITANIUM nano-pore (a) and the interface Ti/ATO (b) figure；
Fig. 5 is the XRD spectrum of chemical Ni-P plating film；
Wherein (a) is result figure of 2 θ when being 0~100 °, (b) result figure when being 40~80 ° for 2 θ.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where spirit of that invention and essence, to modification made by the method for the present invention, step or condition and replaces, belong to the present invention
Range.Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1
For the present embodiment using the high-purity titanium sheet of TA2 as substrate, it is base that the high purity titanium of commercial mill-annealed state, which is cut into sheet titanium,
Body, size: 5mm × 2mm × 0.5mm.
Based on the method for the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition, including successively to high purity titanium
Matrix surface mechanically polished, heat alkali liquid degreasing, anodic oxidation, Pd2+-Sn2+Sensitization activation, Ni-P chemical plating and pulse
The nanocrystalline functional coating of electro-deposition.
Specific step is as follows for the method:
Step 1, mechanical polishing: 800 are successively used#、1200#With 1500#SiC waterproof abrasive paper pure Titanium base is roughly ground,
Then Al is used2O3Antiscuffing paste is polished, after mirror surface, metallography microscope sem observation surface to no marking；
Step 2, heat alkali liquid degreasing: high-purity Titanium base after mechanical polishing is placed in ultrasonic generator, and thermokalite is added
Liquid, treatment temperature are 60 DEG C, are sufficiently washed with deionized water after oscillation, drying for standby；
Step 3, anodic oxidation: in H2SO4In the solution of system, metal base surface, electricity are handled using D.C. regulated power supply
Press 120V, time 10min, 30 DEG C of solution temperature, current density 0.2A/dm2；
Step 4, Pd2+-Sn2+Sensitization activation: being placed in drying in drying box for porous high-purity Titanium base made from step 3, according to
Secondary to be sensitized, be activated, treatment temperature is 45 ± 5 DEG C, time 5min；
Step 5, Ni-P chemical plating: by step 4, treated that high-purity Titanium base is placed in chemical plating solution, pH be 9, temperature
Under the conditions of degree is 35 DEG C, the Pd atom obtained using sensitization activating and reducing is catalyzed in high purity titanium matrix surface generates active site, raw
Long Ni-P film；
The nanocrystalline functional coating of step 6, pulse electrodeposition: using the Ni-P film of step 5 generation as transition zone, and will be high
Pure Titanium base is placed in electrolyte, and bath temperature is set as 30 DEG C, pH value 4, pulse parameter are as follows: current density 1.0A/dm2, arteries and veins
Frequency 1500Hz, make-to-break ratio 3:1 are rushed, electroplating time is adjusted according to thickness of coating demand.
The nanocrystalline functional coating is Ni；The group of the electrolyte is divided into 300g/L NiSO4·H2O, 40g/L
NiSO4·H2O, 35g/L H3BO3, 0.5g/L1.4- butynediols.
The composition of the heat alkali liquid are as follows: 15wt.%NaOH, 20wt.%Na2CO3, the OP-10 surfactant of 0.1g/L,
Remaining is deionized water.
H in step 32SO4The component of system are as follows: 375g/L H2SO4, 62.5g/L HCl, 3g/L H2O2。
Sensitizing solution component in step 4: 30g/L SnCl2, 40g/L HCl, remaining is deionized water；Activating solution component are as follows:
0.4g/L PdCl2, 15g/L HCl, remaining is deionized water.
The component of chemical plating solution in step 5 are as follows: 20g/L NiSO4·H2O, 23g/L NaH2PO4·H2O, 11.7g/L
Na3C6H2O3·H2O, 30g/L NH4Cl。
As shown in Figure 1, titanium surface color shows slightly dark after anodic oxidation, and chemical Ni-P plating is thin compared with pure Titanium base
Film is the defects of silvery white and surface is without peeling.
As shown in Fig. 2, the porous pure titanium matrix aperture obtained after anodized is about 200nm, such major diameter
Nano-pore can meet nanometer crystalline Ni deposition (80~100nm of Ni crystalline substance diameter), have symbiosis elongate member.
As shown in figure 3, by Fig. 3 a it is found that in H2SO4The sun of nano-pore structure is smoothly obtained in system solution through DC voltage
Pole oxidation film, and pore size is uniform；Fig. 3 b is that Pd atom is pinned near nano-pore as trigger point, is subsequent Ni-P film
Growth provides forming core growing point；Fig. 3 c is the Ni-P film of typical born of the same parents' shape feature, stress cracking defect occurs, can pass through subsequent work
Skill is improved.
As shown in figure 4, Titanium base is in H after comparison optimization experiment2SO4It is more equal that diameter size is obtained in system solution
One nano-pore film layer, by Fig. 4 a it is found that cause be not stringent dot matrix feature nano-pore may be due to titanium-based surface injustice
Whole or microstructure texture is inhomogenous and causes.Fig. 4 b is the surface chart of anode oxidation membrane, it is known that: thicknesses of layers is about 1 μm,
And be firmly combined with Titanium base, deposition template is provided for subsequent chemistry plating and electro-deposition.
As shown in figure 5, Ni crystal grain shows certain preferential growth trend Ni in chemical Ni-P plating thin-film process
(010) (002), while nearby there is steamed bun peak at 45 ° in 2 θ, illustrate there are amorphous components, this is conducive to subsequent growth coating and exists
It is refined in structure.
It is manufactured in the present embodiment in titanium substrate anode oxidation film surface chemical plating Ni-P film, grain structure is fine and close, consistency
Height can continue electro-deposition function nano crystalline substance coating in this, as transition zone, good with basal body binding force.Therefore, institute of the present invention
The Ni-P film and its subsequent big thickness electro-deposition nanocrystalline deposit of the porous titanium-based surface of preparation are as function and decorating film
Material it is wear-resistant and in terms of be used widely.
In addition, the present embodiment the method applies also for A1, the active metals such as Mg surface can be according to different anodic oxidations
Technique and variety classes nanocomposite coating prepare uniform functional coating in complex-shaped matrix surface.This technique
Device simple used easy to operate, special standby is suitable for the end such as craftwork and low load tool position surface.
Embodiment 2
The difference from embodiment 1 is that carrying out aging anneal processing, institute before the nanocrystalline functional coating of pulse electrodeposition
Stating treatment temperature is 450 DEG C, time 1.5h, air-cooled with furnace.
Compared compared with embodiment 1, difference is: to including anode oxide film Ni-P chemical plating carry out 450 DEG C ×
The processing of 2.5h aging anneal, main function are to reduce the growth stress of chemical plating Mi-P alloy, reduce craze of coating and be inclined to；
The disperse phases such as the Ni3P generated simultaneously occur to spread with Ti/TiO2 atom in titanium-based nano hole, metallurgical interface can be promoted to combine.
The nanocrystalline functional coating of big thickness (controllable), compact structure, property are prepared in anodic oxidation film surface with this method
Can be excellent, overlay coating and Ti basal body interface binding force are good, can meet low load anti-friction material.The present embodiment the method is also
The anodized surface that can operate with the active metals such as Al, Mg is modified.
Claims (1)
1. a kind of method based on the nanocrystalline functional coating of anodic oxidation porous metals primary surface electro-deposition, which is characterized in that institute
State method include successively metal base surface is mechanically polished, heat alkali liquid degreasing, anodic oxidation, Pd2+-Sn2+Sensitization is lived
Change, Ni-P chemical plating and the nanocrystalline functional coating of pulse electrodeposition；Specific step is as follows: step 1, mechanical polishing: first using SiC
Waterproof abrasive paper roughly grinds metallic matrix, then uses Al2O3Antiscuffing paste is polished, until metallography microscope sem observation surface without
Scratch；Step 2, heat alkali liquid degreasing: the metallic matrix after mechanical polishing is placed in ultrasonic generator, and heat alkali liquid, place is added
Managing temperature is 65~80 DEG C, is sufficiently washed with deionized water after oscillation, drying for standby；Step 3, anodic oxidation: in H2SO4System
Solution in, using D.C. regulated power supply handle metal base surface, 100~120V of voltage, 5~8min of time, solution temperature
30 DEG C, current density 0.2A/dm2~0.4A/dm2；Step 4, Pd2+-Sn2+Sensitization activation: by porous metal matrix made from step 3
Body is placed in drying in drying box, is successively sensitized, is activated, and treatment temperature is 45 ± 5 DEG C, and the time is 3~5min；5th
Step, Ni-P chemical plating: by step 4, treated that metallic matrix is placed in chemical plating solution, pH is 9~10, temperature is 35 DEG C
Under the conditions of, it is catalyzed using the Pd atom that sensitization activating and reducing obtains in metal base surface and generates active site, grow Ni-P film；
The nanocrystalline functional coating of step 6, pulse electrodeposition: the Ni-P film generated using step 5 is set as transition zone, and by metallic matrix
In electrolyte, electrolysis temperature is 30 DEG C, pH value 3~4, double-pulse parameters are as follows: 0.8~1.2A/dm of current density2, pulse frequency
Rate 1500Hz, make-to-break ratio 3:1 adjust electroplating time according to thickness of coating demand；Wherein, the metallic matrix is pure titanium；It is described
Nanocrystalline functional coating is Ni, Cu or its composite deposite；After step 5, before step 6, in the nanocrystalline function of pulse electrodeposition
Aging anneal processing can be carried out to Ni-P film layer before coating, the treatment temperature is 400 ± 25 DEG C, the time is 1.5~
2h, it is air-cooled；The specification of the SiC waterproof abrasive paper is 800#、1200#Or 1500#；The Al2O3Partial size be 5nm；
The composition of the heat alkali liquid are as follows: 15wt.%NaOH, 20wt.%Na2CO3, 0.1g/L OP-10 surfactant, remaining is
Deionized water；
H in step 32SO4The component of system are as follows: 375g/L H2SO4, 62.5g/L HCl, 3~5g/L H2O2Additive；
Sensitizing solution component in step 4: 30g/L SnCl2, 40g/L HCl, remaining is deionized water；Activating solution component are as follows: 0.4g/L
PdCl2, 15g/L HCl, remaining is deionized water；
The component of chemical plating solution in step 5 are as follows: 20g/L NiSO4·H2O, 23g/L NaH2PO4·H2O, 11.7g/L
Na3C6H2O3·H2O, 30g/L NH4Cl；
Wherein, step 3 forms the three-dimensional skeletal type nano-pore of 150-300nm in metal base surface after reaction, and step 4 is anti-
Pd atom is pinned near the nano-pore as catalysis forming core growing point after answering.
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| CN108154004B (en) * | 2017-12-26 | 2020-01-14 | 哈尔滨工业大学 | Transition layer material selection method based on evaluation of bonding force of transition layer on epitaxial film and substrate |
| CN111101162B (en) * | 2019-12-26 | 2021-07-27 | 江苏科技大学 | Method for regulating and controlling nanocrystalline texture growth by using alternating ultrasonic frequency |
| CN111378999B (en) * | 2020-05-12 | 2021-06-08 | 武汉风帆电化科技股份有限公司 | Method for realizing anodic oxide film and phosphorus-nickel alloy composite coating on surface of aluminum alloy |
| CN114836800B (en) * | 2022-05-23 | 2023-09-22 | 江苏科技大学 | Preparation method of Co-Ni-Zn ternary nanocrystalline magnetic alloy and product obtained by preparation method |
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