CN110205629A - A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process - Google Patents

A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process Download PDF

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Publication number
CN110205629A
CN110205629A CN201910527088.5A CN201910527088A CN110205629A CN 110205629 A CN110205629 A CN 110205629A CN 201910527088 A CN201910527088 A CN 201910527088A CN 110205629 A CN110205629 A CN 110205629A
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China
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graphene
cobalt alloy
coating
cadmium cobalt
cadmium
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Chinese (zh)
Inventor
郭崇武
黎小阳
陈康
赖奂汶
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Guangzhou Chao Bang Chemical Co Ltd
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Guangzhou Chao Bang Chemical Co Ltd
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Priority to CN201910527088.5A priority Critical patent/CN110205629A/en
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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
    • 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
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces

Abstract

The invention discloses a kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation processes, the coating structure includes metallic matrix, the cadmium cobalt alloy coating prepared on the metallic matrix, low chromium chromatic passivation layer or the olive passivation layer being formed on the cadmium cobalt alloy coating, and the graphene confining bed formed on the passivation layer.The present invention has the advantages that cadmium cobalt alloy compactness of electroplating is high, corrosion resistance excellent；Low chromium chromatic passivation layer or olive passivation layer tool high corrosion-resistant and self-repairability；Graphene confining bed has high corrosion-resistant and wearability；Therefore, this coating structure has the performances such as especially excellent corrosion resistance, suitable for preparing the protective coating of the strong corrosive environments such as ocean.

Description

A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process
Technical field
The present invention relates to metal plating fields, and in particular to a kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and Preparation process.
Background technique
Marine corrosion is one of the serious problems that navigation and ocean development face in the process, the calamity as caused by marine corrosion There are many difficulty accident case, cause extremely huge loss.In March, 2016, global Investigation On Corrosion report show that the world is average Corrosion loss accounts for about the 3.4%4 of global gross national product, and marine corrosion loss accounts for about the 1/3 of total corrosion loss, if adopted With effective safeguard procedures, can to avoid 25%~40% corrosion loss.Meanwhile marine corrosion causes institution structure to damage Wound, reduced service life, are the major issues for being related to national economy.
With the emergence of China's shipping industry, existing guard technology is no longer satisfied the growing skill of shipping industry Art demand.High corrosion-resistant coating and passivation and sealing technique are developed, the deep-etching caused by solving current tropical ocean environment Problem is of great significance.
Summary of the invention
The purpose of the present invention is to provide a kind of heavy antisepsis type cadmium cobalt alloys and graphene to close coating and preparation process, with Solve the problems, such as that existing coating protection technology does not catch up with development of manufacturing demand.
In order to achieve the above object the present invention adopts the following technical scheme:
A kind of heavy antisepsis type cadmium cobalt alloy and graphene close coating, including metallic matrix, prepare on the metallic matrix Cadmium cobalt alloy coating, the passivation layer formed on the cadmium cobalt alloy coating and the graphene formed on the passivation layer envelope Close layer.
In wherein some embodiments, the cadmium cobalt alloy coating with a thickness of 6~24 μm.
In wherein some embodiments, the passivation layer with a thickness of 0.3~0.8 μm.
In wherein some embodiments, the graphene confining bed with a thickness of 0.3~1 μm.
A kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process, the cadmium cobalt alloy coating is using wide The potassium chloride cadmium Cobalt Alloy Plating technique preparation of Chemical Co., Ltd., Zhou Chao nation exploitation:
20~40g/L of caddy, 2~15g/L of cobalt chloride, 90~160g/L of complexant, 120~180g/L of potassium chloride, brightener 1 ~3mL/L, 20~40mL/L of adjuvant, walk 5~15mL/L of agent；Bath pH value 6.5~7.5,20 DEG C~35 DEG C of coating bath temperature, 0.5~2A/dm of cathode-current density2, the ratio between cathode and annode area are 2 ︰ (1~3), and anode is using cadmium content >=99.97% Cadmium anode plate.
In wherein some embodiments, the passivation layer is prepared using low chromium colorful passivating process.
In wherein some embodiments, the passivation layer is prepared using chromic acid olive passivation technique.
In wherein some embodiments, the graphene confining bed uses the hydroxyl of Guangzhou Chao Bang Chemical Co., Ltd. exploitation The modified sealer preparation of graphene:
The modified sealer of the hydroxyl graphene includes: 15~35 parts of silica solution in parts by weight, and PU 113 is water-soluble 15~35 parts of silane polymer, mass fraction is 4~12 parts of hydroxyl graphene of 4%, the TANAFOAM of Dutch Tuo Na company production It 0.4~0.6 part of S organic silicon defoamer, 0.8~1.5 part of LA13-863 organosilicon levelling agent of Dutch this tal fibre company production, goes 30~50 parts of ionized water；
Deionized water is added to dilute 3 times of preparation hydroxyl graphene confining liquids the modified sealer of the hydroxyl graphene；
Cadmium cobalt alloy plating piece after transpassivation is immersed in hydroxyl graphene confining liquid and forms confining bed.
In wherein some embodiments, the metallic matrix is steel substrate or alloy matrix aluminum.
In wherein some embodiments, when the metallic matrix is alloy matrix aluminum, alloy matrix aluminum and cadmium cobalt alloy are plated It further include the zinc-impregnating layer formed on alloy matrix aluminum, the chemical Ni-plating layer being plated on the zinc-impregnating layer between layer.
In wherein some embodiments, the chemical Ni-plating layer is described using low-phosphorous or middle phosphorus chemistry nickel plating technology preparation Chemical Ni-plating layer is with a thickness of 3~10 μm.
The plug of electric switch needs gold-plated in aerospace and navigating equipment, and the non-gilding of electric switch needs first to change Nickel plating or plating watt nickel are learned, prevents electric switch plug non-gilding when gold-plated that the displacement reaction of gold occurs.
The present invention has the advantages that
1, cadmium cobalt alloy compactness of electroplating of the present invention is high, corrosion resistance excellent, suitable for preparing various strong corrosive environments High corrosion-resistant coating；
2, low chromium chromatic passivation layer and olive passivation layer have high corrosion-resistant and self-repairability, suitable for preparing Aeronautics and Astronautics With the passivation layer of navigation components coating；
3, there is excellent corrosion resistance and wearability using the graphene confining bed of the modified sealer preparation of hydroxyl graphene, can shows Write the service life for improving plating piece；
4, heavy antisepsis type cadmium cobalt alloy and graphene closing coating of the present invention and preparation process, using low chromium chromatic passivation Plating piece, according to GB/T 10125-2012 " artificial atmosphere corrosion test salt spray test " carry out neutral salt spray test 5000h, plating Part surface is generated without white corrosion object, and using the plating piece of olive passivation, according to GB/T 10125-2012, " artificial atmosphere is corroded Test salt spray test " neutral salt spray test 5500h is carried out, plating piece surface is generated without white corrosion object.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, not Inappropriate limitation of the present invention is constituted, in the accompanying drawings:
Fig. 1 is Example 1 and Example 2 of the present invention coating structure schematic diagram；
Fig. 2 is 3 coating structure schematic diagram of the embodiment of the present invention.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention will be described in detail, herein with schematic implementation of the invention Example and explanation are used to explain the present invention, but not as a limitation of the invention.
Embodiment 1:
As shown in Figure 1, a kind of heavy antisepsis type cadmium cobalt alloy and graphene close coating, including steel substrate 1, plating in steel-based Cadmium cobalt alloy coating 2 on body 1, the low chromium chromatic passivation layer 3 being formed on cadmium cobalt alloy coating 2 and to be enclosed in low chromium colored Graphene confining bed 4 on passivation layer 3.
The cadmium cobalt alloy coating 2 with a thickness of 10~12 μm, using the potassium chloride cadmium cobalt alloy of super nation's chemical development Electroplating technology preparation.
The potassium chloride cadmium cobalt alloy plating solution ingredient and operating condition are as follows: caddy 30g/L, cobalt chloride 10g/L, NCC- 617 complexant 140g/L, potassium chloride 160g/L, NCC-617 brightener 2mL/L, NCC-617 adjuvant 30mL/L, NCC-617 are walked Position agent 10g/L, pH are 6.5~7.5,20 DEG C~35 DEG C of temperature, cathode-current density 1.5A/dm2, cathode and annode area it Than for 2 ︰ (1~3), anode is the cadmium plate of cadmium content >=99.97%.
The low chromium chromatic passivation layer 3 is prepared using the HC high protection color passivating agent of super nation's chemical industry:
HC high protects color passivating agent: volume fraction is 2%~4%；
Operating temperature: 20 DEG C~35 DEG C；
Dip time: 5~30s
Passivating solution pH:1.3~2.0；
Stirring: stirring passivating solution or workpiece are swung；
Passivation layer thickness: 0.4~0.6 μm.
The graphene confining bed 4 is prepared using the modified sealer of hydroxyl graphene of super nation's chemical development:
The modified sealer of the hydroxyl graphene includes: 30 parts of silica solution in parts by weight, 113 soluble silane of PU 20 parts of polymer, mass fraction is 4 parts of hydroxyl graphene of 4%, the TANAFOAM S organosilicon defoaming of Dutch Tuo Na company production 0.5 part of agent, 1 part of LA13-863 organosilicon levelling agent, 40 parts of deionized water of Dutch this tal fibre company production；
Deionized water is added to dilute 3 times of preparation hydroxyl graphene confining liquids the modified sealer of the hydroxyl graphene；
Cadmium cobalt alloy plating piece after passivation is immersed in hydroxyl graphene confining liquid and forms confining bed.
The present embodiment is divided into following steps in concrete operations:
1, pre-treatment: to the progress of iron and steel parts 1, " alkali electroless oil removing → washing → pickling → washing → alkalinity anode electrolysis is removed The process of oil → washing → activation → washing ".
2, cadmium plating cobalt alloy: iron and steel parts 1 are prepared after carrying out pre-treatment using potassium chloride cadmium Cobalt Alloy Plating technique Then cadmium cobalt alloy coating 2 carries out dehydrogenation 10h to plating piece at 190 DEG C.
3, be passivated: cadmium cobalt alloy coating 2 carries out " 1.5% nitric acid goes out light → washing → low chromium chromatic passivation → washing " Process obtains passivation layer 3.
4, close: plating piece passivation after carry out " dipping hydroxyl graphene confining liquid → go out slot → drip-dry → blow plating piece bottom off The process of remaining confining liquid → 70 DEG C~90 DEG C drying " obtains graphene confining bed 4.
Embodiment 2:
As shown in Figure 1, a kind of heavy antisepsis type cadmium cobalt alloy and graphene close coating, including steel substrate 1, plating in steel-based Cadmium cobalt alloy coating 2 on body 1, the olive passivation layer 3 being formed on cadmium cobalt alloy coating 2 and it is enclosed in olive passivation Graphene confining bed 4 on layer 3.
The cadmium cobalt alloy coating 2 with a thickness of 10~12 μm, using the potassium chloride cadmium cobalt alloy of super nation's chemical development Electroplating technology preparation.
The potassium chloride cadmium cobalt alloy plating solution ingredient and operating condition are as follows: caddy 25g/L, cobalt chloride 15g/L, NCC- 617 complexant 130g/L, potassium chloride 150g/L, NCC-617 brightener 2mL/L, NCC-617 adjuvant 30mL/L, NCC-617 are walked Position agent 5g/L, pH are 6.5~7.5,20 DEG C~35 DEG C of temperature, cathode-current density 1.5A/dm2, the ratio between cathode and annode area For 2 ︰ (1~3), anode is the cadmium plate of cadmium content >=99.97%.
The olive passivation layer 3 is prepared using the OVG-31 high anti-corrosion olive passivation agent of super nation's chemical industry:
OVG-31 olive passivation agent: 80~120mL/L；
Passivating solution pH:1.0~1.6；
Passivation temperature: 20 DEG C~30 DEG C；
Immerse the time: 30~90s；
Stirring: stirring passivating solution or workpiece are swung；
Passivation layer thickness: 0.5~0.7 μm.
The graphene confining bed 4 is prepared using the modified sealer of hydroxyl graphene of super nation's chemical development:
The modified sealer of the nano-hydroxy graphene includes: 25 parts of silica solution in parts by weight, and PU 113 is water-soluble 25 parts of silane polymer, mass fraction is 6 parts of hydroxyl graphene of 4%, 0.5 part of TANAFOAM S organic silicon defoamer, LA13- 863 1 part of organosilicon levelling agents, 40 parts of deionized water；
Deionized water is added to dilute 3 times of preparation hydroxyl graphene confining liquids the modified sealer of the nano-hydroxy graphene；
Cadmium cobalt alloy plating piece after passivation is immersed in hydroxyl graphene confining liquid and forms confining bed.
The present embodiment is divided into following steps in concrete operations:
1, pre-treatment: to the progress of iron and steel parts 1, " alkali electroless oil removing → washing → pickling → washing → alkalinity anode electrolysis is removed The process of oil → washing → activation → washing ".
2, cadmium plating cobalt alloy: iron and steel parts 1 are prepared after carrying out pre-treatment using potassium chloride cadmium Cobalt Alloy Plating technique Then cadmium cobalt alloy coating 2 carries out dehydrogenation 10h to plating piece at 190 DEG C.
3, be passivated: cadmium cobalt alloy coating 2 carries out the work of " 1.5% nitric acid goes out light → washing → olive passivation → washing " Sequence obtains passivation layer 3.
4, close: plating piece passivation after carry out " dipping hydroxyl graphene confining liquid → go out slot → drip-dry → blow plating piece bottom off The process of remaining confining liquid → 70 DEG C~90 DEG C drying " obtains graphene confining bed 4.
Embodiment 3:
As shown in Fig. 2, a kind of heavy antisepsis type cadmium cobalt alloy and graphene close coating, including alloy matrix aluminum 1, it is formed in aluminium conjunction Zinc-impregnating layer 2 on auri body 1 is plated on zinc-impregnating layer 2 chemical Ni-plating layer 3, the cadmium cobalt alloy coating being plated on chemical Ni-plating layer 3 4,4 olive passivation layer 5 and the graphene confining bed being enclosed on olive passivation layer 5 on cadmium cobalt alloy coating are formed in 6。
The zinc-impregnating layer 2 heavy zinc agent preparation in the AZIN-113 acidic aluminum using super nation's Chemical Manufacture:
Heavy zinc agent in AZIN-113 acidic aluminum: 150~250mL/L；
Operating temperature: 15 DEG C~30 DEG C；
Heavy zinc liquid pH:3.4~4.2；
The heavy zinc time: 20~80s.
The chemical Ni-plating layer 3 is using phosphorus chemistry nickel plating technology preparation in the GG-155 of super nation's chemical industry:
GG-155A:60mL/L；
GG-155B:150mL/L；
Plating solution pH:4.8~5.4；
Operating temperature: 82 DEG C~96 DEG C.
Prepared middle phosphorus chemistry nickel coating with a thickness of 8~10 μm.
The cadmium cobalt alloy coating 4 with a thickness of 8~10 μm, using the potassium chloride cadmium cobalt alloy electricity of super nation's chemical development Depositing process preparation.
The potassium chloride cadmium cobalt alloy plating solution ingredient and operating condition are as follows: caddy 35g/L, cobalt chloride 5g/L, NCC-617 Complexant 150g/L, potassium chloride 180g/L, NCC-617 brightener 2mL/L, NCC-617 adjuvant 30mL/L, NCC-617 walk Agent 10g/L, pH are 6.5~7.5,20 DEG C~35 DEG C of temperature, cathode-current density 1.5A/dm2, the ratio between cathode and annode area For 2 ︰ (1~3), anode is the cadmium plate of cadmium content >=99.97%.
The olive passivation layer 5 is prepared using the OVG-31 high anti-corrosion olive passivation agent of super nation's chemical industry:
OVG-31 olive passivation agent: 80~120mL/L；
Passivating solution pH:1.0~1.6；
Passivation temperature: 20 DEG C~30 DEG C；
Immerse the time: 30~90s；
Stirring: stirring passivating solution or workpiece are swung；
Passivation layer thickness: 0.5~0.7 μm.
The graphene confining bed 6 is prepared using the modified sealer of hydroxyl graphene of super nation's Chemical Manufacture:
The modified sealer of the hydroxyl graphene includes: 20 parts of silica solution in parts by weight, 113 soluble silane of PU 30 parts of polymer, mass fraction is 10 parts of hydroxyl graphene of 4%, 0.5 part of TANAFOAM S organic silicon defoamer, LA13-863 1 part of organosilicon levelling agent, 40 parts of deionized water；
Deionized water is added to dilute 3 times of preparation hydroxyl graphene confining liquids the modified sealer of the hydroxyl graphene；
Cadmium cobalt alloy plating piece after passivation is immersed in hydroxyl graphene confining liquid and forms confining bed.
The present embodiment is divided into following steps in concrete operations:
1, the work of " electrochemical deoiling → washing → etch → washing → go out light → washing " pre-treatment: is carried out to aluminum alloy spare part 1 Sequence.
2, soak zinc: the aluminum alloy spare part 1 through pre-treatment " soak zinc → washing → for the first time and move back zinc → washing → the second The process of secondary leaching zinc → washing " obtains zinc-impregnating layer 2.
3, chemical nickel plating: chemistry is prepared using phosphorus chemistry nickel plating technology in GG-155 by the aluminum alloy spare part 1 of leaching zinc Nickel coating 3.
4, cadmium cobalt alloy coating 4 cadmium plating cobalt alloy: is prepared using potassium chloride cadmium cobalt alloy after components chemical nickel plating.
6, it is passivated: the process that cadmium cobalt alloy coating 4 carries out " 1% nitric acid goes out light → washing → olive passivation → washing " Obtain olive passivation layer 5.
7, close: plating piece passivation after carry out " dipping hydroxyl graphene confining liquid → go out slot → drip-dry → blow plating piece bottom off The process of remaining confining liquid → 70 DEG C~90 DEG C drying " obtains graphene confining bed 6.
Salt spray test:
The plating piece that low chromium chromatic passivation is used in the present embodiment 1, according to GB/T 10125-2012 " artificial atmosphere corrosion test salt Mist test " neutral salt spray test 5000h is carried out, plating piece surface is generated without white corrosion object.
The plating piece that olive passivation is used in the present embodiment 2 and embodiment 3, according to GB/T 10125-2012 " artificial atmosphere Corrosion test salt spray test " neutral salt spray test 5500h is carried out, plating piece surface is generated without white corrosion object.
Combining power test:
Plated item prepared by the present embodiment 1-3, according to JB 2111-1977 " the bonding strength test method of metal cladding ", Binding force of cladding material is measured with thermal shock test method.Plating piece prepared by the technique is placed in heating furnace and is heated to 190 DEG C, taking-up is put Enter in the water of room temperature and cool down suddenly, blistering and falling off do not occur in coating, and the cadmium plating layer binding force is good.
It is provided for the embodiments of the invention technical solution above to be described in detail, specific case used herein The principle and embodiment of the embodiment of the present invention are expounded, the explanation of above embodiments is only applicable to help to understand this The principle of inventive embodiments；At the same time, for those skilled in the art, according to an embodiment of the present invention, in specific embodiment party There will be changes in formula and application range, in conclusion the contents of this specification are not to be construed as limiting the invention.

Claims (10)

1. a kind of heavy antisepsis type cadmium cobalt alloy and graphene close coating, it is characterised in that:
Including metallic matrix, the cadmium cobalt alloy coating that is prepared on metallic matrix, formed on the cadmium cobalt alloy coating it is blunt The graphene confining bed changing layer and being formed on the passivation layer.
2. heavy antisepsis type cadmium cobalt alloy according to claim 1 and graphene close coating, it is characterised in that:
The cadmium cobalt alloy coating with a thickness of 6~24 μm.
3. heavy antisepsis type cadmium cobalt alloy according to claim 1 and graphene close coating, it is characterised in that:
The passivation layer with a thickness of 0.3~0.8 μm.
4. heavy antisepsis type cadmium cobalt alloy according to claim 1 and graphene close coating, it is characterised in that:
The graphene confining bed with a thickness of 0.3~1 μm.
5. a kind of heavy antisepsis type cadmium cobalt alloy and graphene closing coating and preparation process, it is characterised in that:
The cadmium cobalt alloy coating is prepared using the potassium chloride cadmium Cobalt Alloy Plating technique of Guangzhou Chao Bang Chemical Co., Ltd. exploitation:
20~40g/L of caddy, 2~15g/L of cobalt chloride, 90~160g/L of complexant, 120~180g/L of potassium chloride, brightener 1 ~3mL/L, 20~40mL/L of adjuvant, walk 5~15mL/L of agent；Bath pH value 6.5~7.5,20 DEG C~35 DEG C of coating bath temperature, 0.5~2A/dm of cathode-current density2, the ratio between cathode and annode area are 2 ︰ (1~3), and anode is using cadmium content >=99.97% Cadmium anode plate.
6. heavy antisepsis type cadmium cobalt alloy according to claim 5 and graphene closing coating and preparation process, feature exist In:
The passivation layer is prepared using low chromium colorful passivating process or chromic acid olive passivation technique.
7. heavy antisepsis type cadmium cobalt alloy according to claim 5 and graphene closing coating and preparation process, feature exist In:
The graphene confining bed is prepared using the modified sealer of hydroxyl graphene of Guangzhou Chao Bang Chemical Co., Ltd. exploitation:
The modified sealer of the hydroxyl graphene includes: 15~35 parts of silica solution in parts by weight, and PU 113 is water-soluble 15~35 parts of silane polymer, mass fraction is 4~12 parts of hydroxyl graphene of 4%, the TANAFOAM of Dutch Tuo Na company production It 0.4~0.6 part of S organic silicon defoamer, 0.8~1.5 part of LA13-863 organosilicon levelling agent of Dutch this tal fibre company production, goes 30~50 parts of ionized water；
Deionized water is added to dilute 3 times of preparation hydroxyl graphene confining liquids the modified sealer of the hydroxyl graphene；
Cadmium cobalt alloy plating piece after passivation is immersed in hydroxyl graphene confining liquid and forms confining bed.
8. heavy antisepsis type cadmium cobalt alloy according to claim 5 and graphene closing coating and preparation process, feature exist In:
The metallic matrix is steel substrate or alloy matrix aluminum.
9. a kind of heavy antisepsis type cadmium cobalt alloy according to claim 8 and graphene closing coating and preparation process, special Sign is:
It further include in alloy matrix aluminum between alloy matrix aluminum and cadmium cobalt alloy coating when the metallic matrix is alloy matrix aluminum The zinc-impregnating layer of upper formation, the chemical Ni-plating layer being plated on the zinc-impregnating layer.
10. a kind of heavy antisepsis type cadmium cobalt alloy according to claim 9 and graphene closing coating and preparation process, special Sign is:
The chemical Ni-plating layer is using low-phosphorous or middle phosphorus chemistry nickel plating technology preparation, and the chemical Ni-plating layer is with a thickness of 3~10 μm.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724985A (en) * 2019-11-13 2020-01-24 珠海市玛斯特五金塑胶制品有限公司 Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof
CN113373442A (en) * 2021-06-11 2021-09-10 广州超邦化工有限公司 Zinc-cadmium alloy composite coating of aerospace electrical appliance accessory and preparation method thereof
CN113943958A (en) * 2021-11-10 2022-01-18 四川泛华航空仪表电器有限公司 Method for locally plating cadmium and gold on socket sintering assembly

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2334833C1 (en) * 2006-11-21 2008-09-27 Государственное образовательное учреждение высшего профессионального образования "Тюменский государственный нефтегазовый университет" Electrolyte for sedimentation of coatings out of cadmium-cobalt alloy
CN106245071A (en) * 2016-08-31 2016-12-21 广州超邦化工有限公司 Acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology
CN107604390A (en) * 2017-09-11 2018-01-19 重庆立道表面技术有限公司 A kind of cadmium plating walks agent and without hydrogen embrittlement non-cyanide alkali cadmium plating electroplate liquid
CN108385138A (en) * 2018-03-19 2018-08-10 广州超邦化工有限公司 A kind of preparation method for the metal surface coating structure being applicable under Yu Haiyang strong corrosive environment
CN210176975U (en) * 2019-06-17 2020-03-24 广州超邦化工有限公司 Cadmium-cobalt alloy and trivalent chromium passivated coating structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2334833C1 (en) * 2006-11-21 2008-09-27 Государственное образовательное учреждение высшего профессионального образования "Тюменский государственный нефтегазовый университет" Electrolyte for sedimentation of coatings out of cadmium-cobalt alloy
CN106245071A (en) * 2016-08-31 2016-12-21 广州超邦化工有限公司 Acid non-cyanide plating cadmium additive, plating solution preparation and electroplating technology
CN107604390A (en) * 2017-09-11 2018-01-19 重庆立道表面技术有限公司 A kind of cadmium plating walks agent and without hydrogen embrittlement non-cyanide alkali cadmium plating electroplate liquid
CN108385138A (en) * 2018-03-19 2018-08-10 广州超邦化工有限公司 A kind of preparation method for the metal surface coating structure being applicable under Yu Haiyang strong corrosive environment
CN210176975U (en) * 2019-06-17 2020-03-24 广州超邦化工有限公司 Cadmium-cobalt alloy and trivalent chromium passivated coating structure

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724985A (en) * 2019-11-13 2020-01-24 珠海市玛斯特五金塑胶制品有限公司 Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof
CN110724985B (en) * 2019-11-13 2021-03-26 珠海市玛斯特五金塑胶制品有限公司 Sealing treatment liquid, transparent corrosion-resistant film and preparation method thereof
CN113373442A (en) * 2021-06-11 2021-09-10 广州超邦化工有限公司 Zinc-cadmium alloy composite coating of aerospace electrical appliance accessory and preparation method thereof
CN113943958A (en) * 2021-11-10 2022-01-18 四川泛华航空仪表电器有限公司 Method for locally plating cadmium and gold on socket sintering assembly

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