CN101705480B - Chemical modification technology of chemical nickel phosphorus plating alloy coating - Google Patents
Chemical modification technology of chemical nickel phosphorus plating alloy coating Download PDFInfo
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- CN101705480B CN101705480B CN200910075887XA CN200910075887A CN101705480B CN 101705480 B CN101705480 B CN 101705480B CN 200910075887X A CN200910075887X A CN 200910075887XA CN 200910075887 A CN200910075887 A CN 200910075887A CN 101705480 B CN101705480 B CN 101705480B
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Abstract
The invention provides a process for preparing a sodium styrene sulfonate and acrylic acid modified nickel phosphorus plating alloy coating by respectively using a gamma-ray irradiation/chemical grafting technology. A polytetrafluoroethylene emulsion solution, a fluorocarbon cationic surfactant, sodium styrene sulfonate, acrylic acid and the like are used as raw materials, sodium styrene sulfonate and acrylic copolymers are respectively and uniformly grafted in a nickel phosphorus plating alloy coating through the gamma-ray irradiation/chemical grafting technology so as to enable the surface of the coating to be loaded with sulfonic acid groups and carboxylic acid groups which have cation selection penetration property, thereby effectively inhibiting and slowing the migration and the penetration of invasive chloride ions to the inner part of the coating, and improving the property of the conventional nickel phosphorus plating alloy coating resisting point corrosion, gap corrosion and intergranular corrosion caused by the invasive chloride ions. The sodium styrene sulfonate and acrylic acid modified nickel phosphorus plating alloy coating improves the corrosion property of the nickel phosphorus alloy coating in a sodium chloride medium, and expands the application to the fields of petrochemical complex, pump manufacture industry and the like.
Description
Technical field
The present invention relates to the corrosion resisting property improvement of chemical nickeling phosphorus alloy film; Particularly relating to reagent such as a kind of employing ptfe emulsion, fluorine carbon type cats product, SSS and vinylformic acid is raw material; Use gamma-ray irradiation/Chemical Grafting Technique, the preparation technology who nickel-phosphorus alloy coating is carried out modification.
Background technology
Corrosion of Metallic Materials such as iron and steel spread all over each Application Areas of national economy; All can bring enormous economic loss every year; The investigation of developed country shows; The annual financial loss that causes because of metallic material corrosion accounts for 2%～4% of gross national product, and the financial loss that China every year causes because of corrosion is also above 20,000,000,000 yuan.Fully carrying out Corrosion of Metallic Materials and protected working, is the important behave that ensures a series of key subjects such as utilization of resources, environment protection, normal production and new technology research and development.Thereby, actively research and develop anti-corrosion novel material and anticorrosion new technology, reducing and corroding the financial loss that causes is the key subjects that current urgent need solves.
Be the loss that effective mitigate corrosion is caused, the main at present corrosion resisting property that adopts surface coating technique to improve metallic substance promptly stops water, air and corrosive medium to contact its corrosion resisting property of raising with metallic substance with coating.Many scholars adopt technology such as plating, electroless plating, compound plating, vapour deposition, electrophoretic painting with metals such as Ni, Cr, Zn, alloy layers such as Ni-P, TiN, SiO
2, TiO
2Deng sull, and organic polymer plating such as epoxy resin forms resist in the metallic surface.Wherein, The research of chemical nickel phosphorus plating (Ni-P) alloy layer is comparatively extensive, and Ni-P coating hole is few, thickness is even, hardness is high, surface smoothness and all better with the bonding force of matrix, and its structure is a non-crystalline state; There are not crystal boundary, defective etc., have higher erosion resistance.
Chemical plating nickel-phosphorus alloy is owing to excellent solidity to corrosion is widely used in the various industrial environments, but the different alloy layer solidity to corrosion in different corrosive mediums and environment of phosphorus content has tangible difference, decide according to concrete application conditions.The Ni-P alloy layer of high phosphorus amount (＞10wt%) be amorphous structure; Coating does not have grain mark; And in air, be prone to form the passive film of vitreous state; Can effectively stop galvanic corrosion to take place, so generally speaking high phosphorus coating has been considered to better solidity to corrosion, acidic conditions is selected the Ni-P coating of high content of phosphorus usually for use.The solidity to corrosion of the Ni-P coating of low phosphorus content is more satisfactory under the highly basic condition, but its solidity to corrosion is different with corrosive medium.
In numerous corrosion protection coatings; The Ni-P chemical plating has good anti-corrosion, has been widely used in the anticorrosion research of multiple metallic substance, but the solidity to corrosion of conventional Ni-P coating in Oxidant is relatively poor; And the corrosion resisting property of long period of soaking in sodium chloride solution is also undesirable; Thereby be matrix with the Ni-P protective coating, it is carried out modification, it is significant to research and develop the modification nickel-phosphorus coating novel, that corrosion resisting property is good.As with nickel-phosphorus coating at 1%CrO
3Solution impregnation 15min carries out Passivation Treatment, and its salt fog resistance experiment effect improves about 1 times; After first flash copper on the steel substrate, plate the Ni-P alloy again and can improve solidity to corrosion, can also improve electroconductibility and shock-resistance simultaneously; Adopt dual nickel-phosphorus coating, promptly on high phosphor alloy coating, plate low phosphor alloy coating again,, can play the effect of sacrificial anode because the current potential higher phosphorous of low-phosphorous coating is more negative; Add alloying elements such as Cu, Zn, Sn, MO, W, Cr and Re, obtain the polynary coating of nickel phosphorus to improve its corrosion resisting property; Adopt chemical nickel phosphorus plating and various inert particulate codeposition, can obtain the brand-new composite deposite of function, like Ni-P-Al
2O
3, Ni-P-SiC, Ni-P-Cr
2O
3, composite deposites such as Ni-P-PTFE, Ni-P-graphite, thereby improve solidity to corrosion, wear resistance and the lubricity of nickel-phosphorus alloy coating.
Chemical nickeling phosphorus alloy film belongs to galvanic protection coating concerning most of iron alloys and aluminum alloy materials, but will guarantee that nickel-phosphorus coating has excellent corrosion resistant performance, must make it on the metallic surface, form complete blocking layer.The corrosion of nickel-phosphorus coating mainly contains two kinds of forms, and a kind of is uniform corrosion, and another kind is that spot corrosion takes place at coating hole place.If nickel-phosphorus coating exists hole or defective will have a strong impact on the protection effect of coating, for avoiding coating hole or defective appear, postprocessing working procedures such as the pre-treatment that must pay close attention to metallic substance and plating back nickel-phosphorus coating sealing of hole.
Be used for etch-proof Application Areas from nickel-phosphorus alloy coating and see, its protection against corrosion emphasis is the local corrosion of sodium chloride medium.Cl ions is the aggressiveness ion; It permeates to metallic matrix through the surface of nickel-phosphorus coating easily; When it contacts with protected metallic substance, cause spot corrosion, crevice corrosion and the intergranular corrosion of metallic substance usually, thereby cause the antiseptic property forfeiture of nickel-phosphorus alloy coating.At present; Most scholars is still implemented the nickel-phosphorus coating sealing of hole and is handled or adopt nickel phosphorus multi-elements alloying coating and nickel-phosphorus composite deposit; Suppress in the corrosive medium aggressiveness cl ions to the destruction of metallic substance through the mechanical barrier effect; Fundamentally do not eliminate the harm of cl ions, finally limited the application of nickel-phosphorus coating and composite deposite thereof in each field to metallic substance.
To fundamentally eliminate the harm that cl ions exists metallic substance; Should stop it to pass through nickel-phosphorus coating to metallic surface migration infiltration; If at sulfonic acid or the vinylformic acid functional group that the nickel-phosphorus alloy coating surface grafting has the cation selective penetrating quality, this functional group will suppress the selection infiltration of cl ions, stop cl ions to pass through nickel-phosphorus alloy coating to the metal material matrix surface seepage; Thereby eliminated the potential hazard of cl ions, effectively improved the antiseptic property of nickel-phosphorus alloy coating.
Summary of the invention
In order effectively to improve the performance of nickel-phosphorus alloy coating anti-chlorine ion corrosion; The present invention provides a kind of preparation technology of grafting modification of nickel-phosphorus alloy coating; Through gamma-ray irradiation/Chemical Grafting Technique; Evenly apply SSS and XPA respectively on nickel-phosphorus alloy coating surface, make the nickel-phosphorus alloy coating surface evenly grafting have the diactinic sulfonic acid group of cation selective and carboxylic-acid functional group, effectively suppress and slow down that the aggressiveness cl ions permeates to protected metal material surface migration through nickel-phosphorus alloy coating in the corrosive medium; Effectively avoid the metallic material local corrosive to take place, improved the corrosion resisting property of nickel-phosphorus alloy coating.
1. the preparation technology of a SSS modification ni-p electroless plating alloy layer is:
1) preparation of chemical nickeling phosphorus alloy film:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate, the consisting of of chemical plating fluid: single nickel salt 20～30g/L, sodium hypophosphite 20～35g/L; Lactic acid 15～25g/L, sodium acetate 4～8g/L, Sodium Fluoride 2～4g/L; Fluorine carbon type cats product 0.2～0.4g/L, its model is FC-4, ptfe emulsion 15～30g/L; Wherein the quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, at first in deionized water, single nickel salt, sodium hypophosphite, lactic acid, sodium acetate, Sodium Fluoride dissolving is mixed; Using the pH value of ammoniacal liquor adjustment solution again is 4.6～5.2, then fluorine carbon type cats product and ptfe emulsion is mixed, after fully stirring; Slowly join in the above-mentioned plating bath and fully and stir, bath temperature is slowly raise; Metallic substance is selected the Q235 carbon steel; At first with its polishing, oil removing, acid-wash activation, when treating that bath temperature is increased to 85 ℃～90 ℃, the Q235 carbon steel is positioned over carries out plating in the plating bath; Keeping bath temperature is 85 ℃～90 ℃; Behind the 90min carbon steel is taken out from plating bath, successively it is rinsed well, dry at 80 ℃～120 ℃ then with hot water, cold water and deionized water.
2) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film:
The chemical nickeling phosphorus alloy film of step 1) preparation is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating.
3) the SSS chemical modification liquid that grafting modification adopted that is used for the ni-p electroless plating alloy layer consists of:
A. SSS 100～150g/L, acrylic amide 4～7g/L, methylene-bisacrylamide 5～8g/L;
B. solvent for use is deionized water or zero(ppm) water;
C. being formulated in the air of chemical modification liquid carried out, or under the protection of inert nitrogen gas, carries out;
D. the addition sequence of each reagent is: SSS, acrylic amide, methylene-bisacrylamide.
4) adopt gamma-ray irradiation/Chemical Grafting Technique to prepare the preparation process of SSS modified chemical plating nickel-phosphorus alloy coating:
A. with using in the step " 2) "
60The ni-p electroless plating alloy layer that Co gamma-rays pre-irradiation is handled is dipped in the described chemical modification liquid of step " 3) ", and soak time is 30～45min;
B. chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove its surperficial excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
C. after thermal treatment finishes, chemical nickeling phosphorus alloy film is at first used 95% ethanolic soln soaking at room temperature 30min, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last.
2. the preparation technology of acrylic acid modified ni-p electroless plating alloy layer is:
1) preparation of chemical nickeling phosphorus alloy film:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate, the consisting of of chemical plating fluid: single nickel salt 20～30g/L, sodium hypophosphite 20～35g/L; Lactic acid 15～25g/L, sodium acetate 4～8g/L, Sodium Fluoride 2～4g/L; Fluorine carbon type cats product 0.2～0.4g/L, its model is FC-4, ptfe emulsion 15～30g/L; Wherein the quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, at first in deionized water, single nickel salt, sodium hypophosphite, lactic acid, sodium acetate, Sodium Fluoride dissolving is mixed; Using the pH value of ammoniacal liquor adjustment solution again is 4.6～5.2, then fluorine carbon type cats product and ptfe emulsion is mixed, after fully stirring; Slowly join in the above-mentioned plating bath and fully and stir, bath temperature is slowly raise; Metallic substance is selected the Q235 carbon steel; At first with its polishing, oil removing, acid-wash activation, when treating that bath temperature is increased to 85 ℃～90 ℃, the Q235 carbon steel is positioned over carries out plating in the plating bath; Keeping bath temperature is 85 ℃～90 ℃; Behind the 90min carbon steel is taken out from plating bath, successively it is rinsed well, dry at 80 ℃～120 ℃ then with hot water, cold water and deionized water.
2) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film:
The chemical nickeling phosphorus alloy film of step 1) preparation is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating.
3) the vinylformic acid chemical modification liquid that grafting modification adopted that is used for the ni-p electroless plating alloy layer consists of:
A. vinylformic acid 80～120g/L, acrylic amide 4～7g/L, methylene-bisacrylamide 5～8g/L;
B. solvent for use is deionized water or zero(ppm) water;
C. being formulated in the air of chemical modification liquid carried out, or under the protection of inert nitrogen gas, carries out;
D. vinylformic acid neutralizes with sodium hydroxide solution, and degree of neutralization is 75%～85%;
E. the addition sequence of each reagent is: neutral vinylformic acid, acrylic amide, methylene-bisacrylamide.
4) adopt gamma-ray irradiation/Chemical Grafting Technique to prepare the preparation process of acrylic acid modified ni-p electroless plating alloy layer:
A. with using in the step " 2) "
60The chemical nickeling phosphorus alloy film that the Co gamma-ray irradiation is handled is dipped in the described chemical modification liquid of step " 3) ", and soak time is 30～45min;
B. chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove film surface excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
C. after thermal treatment finishes, chemical nickeling phosphorus alloy film is at first used 95% ethanolic soln soaking at room temperature 30min, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last.
The present invention is suitable equally to adopting reagent such as ptfe emulsion, fluorine carbon type cats product, SSS, vinylformic acid to carry out the modification of nickel-phosphorus alloy coating of other types carbon steel, duraluminum, magnalium, plastics and ceramic surface.The present invention is to being main agents with ptfe emulsion, fluorine carbon type cats product, SSS, vinylformic acid, and the surface-treated that using plasma initiation/Chemical Grafting Technique is used for nickel-phosphorus alloy coating is suitable for too.
The invention has the beneficial effects as follows: this even respectively grafting has the gamma-rays pre-irradiation/Chemical Grafting Technique of diactinic sulfonic acid of cation selective and carboxylic-acid functional group on ni-p electroless plating alloy layer surface; Have advantages such as simple to operate, that grafting is even; Improve the conventional chemical plating nickel-phosphorus alloy coating corrosive of anti-sodium chloride medium performance, improved the performance of the anti-local corrosion of nickel-phosphorus alloy coating.This invention has realized that nickel-phosphorus alloy coating effectively suppresses and slow down the migration infiltration of aggressiveness cl ions; Effectively eliminated the corrosion harmfulness that cl ions exists metallic substance in the corrosive medium; Improved the performance of the spot corrosion of nickel-phosphorus alloy coating resisting chloride ion penetration, crevice corrosion and intergranular corrosion, expanded the application of nickel-phosphorus alloy coating in fields such as petrochemical complex, robot calculator, device fabrication and printings.
Embodiment
Following mask body combines embodiment, specifies to adopt gamma-rays pre-irradiation/Chemical Grafting Technique, uses SSS and vinylformic acid respectively, the preparation technology of modification ni-p electroless plating alloy layer.
Embodiment
1, gamma-ray irradiation/Chemical Grafting Technique prepares the technology of SSS modification ni-p electroless plating alloy layer
(1) chemical nickel phosphorus plating coating prepares the preparation of used plating bath:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate; The process for preparation of 1L plating bath is: in beaker; With 25g single nickel salt, 20g lactic acid, 5g sodium acetate and 2.5g Sodium Fluoride with deionized water or dissolved in distilled water; Temperature is 40 ℃～50 ℃ during dissolving, treat that each reagent dissolves fully after, bath temperature is cooled to room temperature;
In another beaker, the 30g sodium hypophosphite is at room temperature dissolved with proper amount of deionized water or zero(ppm) water;
Above-mentioned two kinds of solution are mixed, and fully stir, regulate the pH value of plating bath then with ammoniacal liquor, the pH value that makes plating bath is 4.8;
With 0.25g fluorine carbon type cats product and 25g ptfe emulsion thorough mixing; Fluorine carbon type cats product model is FC-4; The quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, and then tensio-active agent and ptfe emulsion mixed solution slowly being joined above-mentioned pH value is in 4.8 the plating bath; Magnetic agitation makes each component thorough mixing in the plating bath;
After treating that tensio-active agent and ptfe emulsion mixed solution add fully, bath temperature slowly is elevated to 85 ℃～90 ℃.
(2) preparation of chemical nickeling phosphorus alloy film
With the Q235 carbon steel polish successively, oil removing, acid-wash activation handle, and be clean with deionized water or distilled water flushing again, be positioned over rapidly then and carry out plating in the chemical plating fluid, magnetic agitation, keeping bath temperature is 85 ℃～90 ℃;
Behind the 90min, Q235 carbon steel plating piece is taken out from plating bath, successively it is rinsed well, dry processing at 80 ℃～120 ℃ then with hot water, cold water and deionized water.
(3) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film
Chemical nickeling phosphorus alloy film is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating.
(4) preparation of SSS chemical modification liquid
The process for preparation of 1L SSS chemical modification is: with the SSS of 120g with deionized water or dissolved in distilled water;
After treating that SSS dissolves fully, successively 5g acrylic amide and 6g methylene-bisacrylamide are joined in the above-mentioned solution, stir fully dissolving, make its thorough mixing;
In the process for preparation of chemical modification liquid, guarantee that solution temperature can not be above 50 ℃.
(5) preparation of SSS modification ni-p electroless plating alloy layer
With using in the step " (3) "
60The chemical nickeling phosphorus alloy film that Co gamma-rays pre-irradiation is handled is dipped in the described chemical modification liquid of step " (4) ", and soak time is 30～45min;
Then chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove its surperficial excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
After thermal treatment finishes, chemical nickeling phosphorus alloy film was at first used 95% ethanolic soln soaking at room temperature 30 minutes, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last.
2, gamma-ray irradiation/Chemical Grafting Technique prepares the technology of acrylic acid modified chemical nickel phosphorus plating coating
(1) chemical nickel phosphorus plating coating prepares the preparation of used plating bath:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate; The process for preparation of 1L plating bath is: in beaker; With 25g single nickel salt, 20g lactic acid, 5g sodium acetate and 2.5g Sodium Fluoride with deionized water or dissolved in distilled water; Temperature is 40 ℃～50 ℃ during dissolving, treat that each reagent dissolves fully after, bath temperature is cooled to room temperature;
In another beaker, the 30g sodium hypophosphite is at room temperature dissolved with proper amount of deionized water or zero(ppm) water;
Above-mentioned two kinds of solution are mixed, and fully stir, regulate the pH value of plating bath then with ammoniacal liquor, the pH value that makes plating bath is 4.8;
With 0.25g fluorine carbon type cats product and 25g ptfe emulsion thorough mixing; Fluorine carbon type cats product model is FC-4; The quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, and then tensio-active agent and ptfe emulsion mixed solution slowly being joined above-mentioned pH value is in 4.8 the plating bath; Magnetic agitation makes each component thorough mixing in the plating bath;
After treating that tensio-active agent and ptfe emulsion mixed solution add fully, bath temperature slowly is elevated to 85 ℃～90 ℃.
(2) preparation of chemical nickeling phosphorus alloy film
With the Q235 carbon steel polish successively, oil removing, acid-wash activation handle, and be clean with deionized water or distilled water flushing again, be positioned over rapidly then and carry out plating in the chemical plating fluid, magnetic agitation, keeping bath temperature is 85 ℃～90 ℃;
Behind the 90min, Q235 carbon steel plating piece is taken out from plating bath, successively it is rinsed well, dry processing at 80 ℃～120 ℃ then with hot water, cold water and deionized water.
(3) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film
Chemical nickeling phosphorus alloy film is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating.
(4) preparation of vinylformic acid chemistry modification liquid
The process for preparation of 1L vinylformic acid chemistry modification is: the vinylformic acid of 100g is neutralized with aqueous sodium hydroxide solution, and degree of neutralization is 80%;
After treating that solution temperature is cold slightly, add acrylic amide 5g, stir fully dissolving;
And then the 6g methylene-bisacrylamide joined in the mixed solution fully dissolving, make its thorough mixing;
In the process for preparation of chemical modification liquid, guarantee that solution temperature can not be above 50 ℃.
(5) preparation of acrylic acid modified chemical nickel phosphorus plating coating
With using in the step " (3) "
60The chemical nickeling phosphorus alloy film that Co gamma-rays pre-irradiation is handled is dipped in the described chemical modification liquid of step " (4) ", and soak time is 30～45min;
Then chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove its surperficial excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
After thermal treatment finishes, chemical nickeling phosphorus alloy film was at first used 95% ethanolic soln soaking at room temperature 30 minutes, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last.
Claims (2)
1. the preparation technology of a SSS modification ni-p electroless plating alloy layer makes to be grafted with the diactinic functional group of sulfonic acid of cation selective in the nickel-phosphorus alloy coating, and it is characterized in that: this preparation technology may further comprise the steps:
1) preparation of chemical nickeling phosphorus alloy film:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate, the consisting of of chemical plating fluid: single nickel salt 20～30g/L, sodium hypophosphite 20～35g/L; Lactic acid 15～25g/L, sodium acetate 4～8g/L, Sodium Fluoride 2～4g/L; Fluorine carbon type cats product 0.2～0.4g/L, its model is FC-4, ptfe emulsion 15～30g/L; Wherein the quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, at first in deionized water, single nickel salt, sodium hypophosphite, lactic acid, sodium acetate, Sodium Fluoride dissolving is mixed; Using the pH value of ammoniacal liquor adjustment solution again is 4.6～5.2, then fluorine carbon type cats product and ptfe emulsion is mixed, after fully stirring; Slowly join in the above-mentioned plating bath and fully and stir, bath temperature is slowly raise; Metallic substance is selected the Q235 carbon steel; At first with its polishing, oil removing, acid-wash activation, when treating that bath temperature is increased to 85 ℃～90 ℃, the Q235 carbon steel is positioned over carries out plating in the plating bath; Keeping bath temperature is 85 ℃～90 ℃; Behind the 90min carbon steel is taken out from plating bath, successively it is rinsed well, dry at 80 ℃～120 ℃ then with hot water, cold water and deionized water;
2) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film:
The chemical nickeling phosphorus alloy film of step 1) preparation is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating;
3) the SSS chemical modification liquid that grafting modification adopted that is used for the ni-p electroless plating alloy layer consists of:
A. SSS 100～150g/L, acrylic amide 4～7g/L, methylene-bisacrylamide 5～8g/L;
B. solvent for use is deionized water or zero(ppm) water;
C. being formulated in the air of chemical modification liquid carried out, or under the protection of inert nitrogen gas, carries out;
D. the addition sequence of each reagent is: SSS, acrylic amide, methylene-bisacrylamide;
4) adopt gamma-ray irradiation/Chemical Grafting Technique to prepare the preparation process of SSS modified chemical plating nickel-phosphorus alloy coating:
A. with being dipped in the described chemical modification liquid of step " 3) " with the ni-p electroless plating alloy layer of 60Co gamma-rays pre-irradiation processing in the step " 2) ", soak time is 30～45min;
B. chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove its surperficial excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
C. after thermal treatment finishes, chemical nickeling phosphorus alloy film is at first used 95% ethanolic soln soaking at room temperature 30min, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last;
2. the preparation technology of an acrylic acid modified ni-p electroless plating alloy layer makes to be grafted with cation selective through performance carboxylic-acid functional group in the nickel-phosphorus alloy coating, and it is characterized in that: this preparation technology may further comprise the steps:
1) preparation of chemical nickeling phosphorus alloy film:
Adopt Ni-P to prepare the nickel-phosphorus alloy coating of surface doping tetrafluoroethylene particulate, the consisting of of chemical plating fluid: single nickel salt 20～30g/L, sodium hypophosphite 20～35g/L; Lactic acid 15～25g/L, sodium acetate 4～8g/L, Sodium Fluoride 2～4g/L; Fluorine carbon type cats product 0.2～0.4g/L, its model is FC-4, ptfe emulsion 15～30g/L; Wherein the quality percentage composition of tetrafluoroethylene is 60%, and particle diameter is 0.1 μ m～0.5 μ m, at first in deionized water, single nickel salt, sodium hypophosphite, lactic acid, sodium acetate, Sodium Fluoride dissolving is mixed; Using the pH value of ammoniacal liquor adjustment solution again is 4.6～5.2, then fluorine carbon type cats product and ptfe emulsion is mixed, after fully stirring; Slowly join in the above-mentioned plating bath and fully and stir, bath temperature is slowly raise; Metallic substance is selected the Q235 carbon steel; At first with its polishing, oil removing, acid-wash activation, when treating that bath temperature is increased to 85 ℃～90 ℃, the Q235 carbon steel is positioned over carries out plating in the plating bath; Keeping bath temperature is 85 ℃～90 ℃; Behind the 90min carbon steel is taken out from plating bath, successively it is rinsed well, dry at 80 ℃～120 ℃ then with hot water, cold water and deionized water;
2) the gamma-ray irradiation pre-treatment of chemical nickeling phosphorus alloy film:
The chemical nickeling phosphorus alloy film of step 1) preparation is at first used ultrasonic cleaning 3～5min; After treating that its surface is dried, use then
60The Co gamma-rays carries out radiation treatment in air, irradiation intensity is 40～60kGy, and irradiation time is 30～60min, introduces superoxide and radical on the tetrafluoroethylene particulate in coating;
3) the vinylformic acid chemical modification liquid that grafting modification adopted that is used for the ni-p electroless plating alloy layer consists of:
A. vinylformic acid 80～120g/L, acrylic amide 4～7g/L, methylene-bisacrylamide 5～8g/L;
B. solvent for use is deionized water or zero(ppm) water;
C. being formulated in the air of chemical modification liquid carried out, or under the protection of inert nitrogen gas, carries out;
D. vinylformic acid neutralizes with sodium hydroxide solution, and degree of neutralization is 75%～85%;
E. the addition sequence of each reagent is: neutral vinylformic acid, acrylic amide, methylene-bisacrylamide;
4) adopt gamma-ray irradiation/Chemical Grafting Technique to prepare the preparation process of acrylic acid modified ni-p electroless plating alloy layer:
A. with using in the step " 2) "
60The chemical nickeling phosphorus alloy film that the Co gamma-ray irradiation is handled is dipped in the described chemical modification liquid of step " 3) ", and soak time is 30～45min;
B. chemical nickeling phosphorus alloy film is taken out from chemical modification liquid; Remove film surface excessive solution, place well heater to heat-treat, keep 80 ℃～120 ℃ of temperature; Heat treatment time is 20～30min, and thermal treatment is carried out in air or under the protection of inert gas atmosphere;
C. after thermal treatment finishes, chemical nickeling phosphorus alloy film is at first used 95% ethanolic soln soaking at room temperature 30min, rinse well with deionized water then, under 80 ℃～120 ℃ temperature, dry at last.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910075887XA CN101705480B (en) | 2009-11-03 | 2009-11-03 | Chemical modification technology of chemical nickel phosphorus plating alloy coating |
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| CN200910075887XA CN101705480B (en) | 2009-11-03 | 2009-11-03 | Chemical modification technology of chemical nickel phosphorus plating alloy coating |
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| CN102211077B (en) * | 2011-03-01 | 2014-02-26 | 北京市射线应用研究中心 | Method for preparing organic film on surface of NiTi alloy |
| CN102400118B (en) * | 2011-11-18 | 2013-06-26 | 钢铁研究总院 | Preparation method of nickel phosphorus alloy plating on surface of sintered neodymium iron boron permanent magnet |
| CN103834936A (en) * | 2012-11-27 | 2014-06-04 | 大连经济技术开发区圣洁真空技术开发有限公司 | Ni-P chemical composite plating process |
| CN103290397B (en) * | 2013-06-08 | 2016-08-10 | 广州市特种承压设备检测研究院 | Plating solution, preparation method and the anti-corrosive safety valve of a kind of relief valve surface super hydrophobic chemical deposit |
| CN103774125B (en) * | 2014-02-10 | 2016-05-04 | 杭州广荣科技有限公司 | A kind of heat treatment method of Electroless Nickel Plating of Aluminum Alloy phosphorus alloy layer |
| JP6405109B2 (en) * | 2014-04-11 | 2018-10-17 | 東洋鋼鈑株式会社 | Surface treatment substrate |
| TWI569931B (en) * | 2014-11-06 | 2017-02-11 | Sdi Corp | Stapler and its gutter structure |
| CN105624656B (en) * | 2015-12-30 | 2018-05-01 | 大连大学 | A kind of chemical Ni-P plating/Ni-Mo-P-PTFE composite structure platings and preparation method thereof |
| CN108796478B (en) * | 2018-06-29 | 2020-07-07 | 林忠华 | Electroless nickel-tin-tungsten-phosphorus amorphous multifunctional alloy plating solution and plating layer thereof |
| CN111394716A (en) * | 2019-01-03 | 2020-07-10 | 泰科电子(上海)有限公司 | Multi-coating stacked structure, preparation method and application thereof |
| CN111304639A (en) * | 2020-03-12 | 2020-06-19 | 佛山市众之助新材料科技有限公司 | Oil-free piston medical air compressor cylinder body and surface treatment process thereof |
| CN115821240A (en) * | 2022-11-30 | 2023-03-21 | 常州联德陶业有限公司 | Processing technology of scale-proof hydrophobic coating of ceramic heater and Ni-P/PTFE composite chemical plating solution thereof |
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