CN105908113A - Plating assistant agent for zinc-aluminum-nickel-rare earth-alloy hot-dip plating and technological method - Google Patents
Plating assistant agent for zinc-aluminum-nickel-rare earth-alloy hot-dip plating and technological method Download PDFInfo
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- CN105908113A CN105908113A CN201610298566.6A CN201610298566A CN105908113A CN 105908113 A CN105908113 A CN 105908113A CN 201610298566 A CN201610298566 A CN 201610298566A CN 105908113 A CN105908113 A CN 105908113A
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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Abstract
The invention provides a plating assistant agent for zinc-aluminum-nickel-rare earth-alloy hot-dip plating and a technological method. The plating assistant agent comprises the following components of an A solution containing zinc chloride, ammonium chloride, stannous chloride and urotropin and a B solution containing ethyl alcohol, a nonionic surfactant and a cationic surfactant, wherein the plating assistant agent is obtained by mixing the A solution and the B solution. By using the plating assistant agent, skip plating can be effectively avoided; and the surface quality of a plating layer is obviously improved; the yield of a plated article is improved; and the corrosion-resistance of the plating layer can be obviously improved. The plating assistant agent does not contain fluorinion which is harmful to the environment, and requirement of environment protection is met.
Description
Technical field
The invention belongs to ferrous materials anticorrosion technique field, relate to steel material surface plating technic technology, be specifically related to a kind of special fluxing agent formula being applicable to thermal dip plating of steel zinc-aluminium nickel rare earth alloy coating and or immersion method.
Background technology
Galvanizing can significantly improve iron and steel weather-resistance, is one of the Main Means of the anti-atmospheric corrosion of iron and steel, is widely used in engineering.The protective effect of zinc coat includes: be on the one hand to provide physical protection barrier to iron and steel, stops that it is eroded by extraneous corrosive medium；On the other hand as sacrificial anode, ferrous materials can be carried out cathodic protection.Along with science and technology and the development of modern industry, galvanizing product is had higher requirement.In order to make the acid resistance salt air corrosion performance (especially under the atmospheric environment that south industrial pollution is heavier) of steel piece Zinc coat improve, during galvanizing, the alloying elements such as aluminum, nickel and rare earth are added in zinc is bathed, so can reduce the zinc oxidation on zinc liquid surface, obtaining surfacing, the coating of light, the decay resistance of coating have also been obtained raising.
Zinc-aluminium nickel rare earth alloy coating has the performance of excellence, but owing to the use of existing fluxing agent can cause steel piece surface serious plating leakage phenomenon occur, makes hot-dip aluminum zinc nickel rare earth alloy layer be limited by very large in production application.Therefore, research and develop the special fluxing agent of a kind of applicable hot-dip aluminum zinc nickel rare earth alloy just to become urgent need and solve the technical problem that.
Summary of the invention
It is an object of the invention to overcome serious plating leakage problem present in prior art, and preferably go out a kind of to help effective, moderate, the hot-dip aluminum zinc nickel rare earth alloy fluxing agent of environmental protection of plating and process by acid salt spray test.
For reaching above-mentioned purpose, present invention employs techniques below scheme:
A kind of hot-dip aluminum zinc nickel rare earth alloy fluxing agent, this fluxing agent includes following components: the nonionic surfactant of the ethanol of the hexamethylenamine of the stannous chloride of the ammonia chloride of zinc chloride, 12.5～50g/L, 7.5～40g/L, 0.05～0.4g/L, 25～150g/L, 0.50～the 2.40g/L of 10～70g/L and the cationic surfactant of 0.75～7g/L.
Preferably, described fluxing agent includes following components: the nonionic surfactant of the ethanol of the hexamethylenamine of the stannous chloride of the ammonia chloride of zinc chloride, 20～50g/L, 10～40g/L, 0.1～0.4g/L, 25～150g/L, 0.80～the 2.40g/L of 10～70g/L and the cationic surfactant of 0.80～5g/L.
Described fluxing agent is the aqueous solution formulated by water and zinc chloride, ammonium chloride, stannous chloride, ethanol, hexamethylenamine, nonionic surfactant and cationic surfactant.
Described nonionic surfactant is selected from alkylphenol polyoxyethylene, and described cationic surfactant is selected from quaternary cationics (preferably alkyl dimethyl benzyl ammonium type, such as myristyl benzyl dimethyl ammonium chloride).
A kind of hot-dip aluminum zinc nickel rare earth alloy technology method, comprises the following steps:
1) preparation fluxing agent
Described fluxing agent is made up of water and the following components that is dissolved in the water: the nonionic surfactant of the ethanol of the hexamethylenamine of the stannous chloride of the ammonia chloride of zinc chloride, 12.5～50g/L, 7.5～40g/L, 0.05～0.4g/L, 25～150g/L, 0.50～the 2.40g/L of 10～70g/L and the cationic surfactant of 0.75～7g/L；
2) will clean steel piece immersion fluxing agent carry out helping plating, the described temperature helping plating is 40～60 DEG C, the time helping plating is 20～50s, steel piece after helping plating is carried out drying and processing, make the uniform fluxing agent film of steel piece surface attachment one layer, the more melted zinc-aluminium nickel rare earth alloy liquid of immersion carry out hot-dip.
Described step 1) specifically include following steps:
1.1) by ammonium chloride, zinc chloride, stannous chloride and hexamethylenamine water dissolution, solution A is obtained；
1.2) by ethanol, nonionic surfactant and cationic surfactant water dissolution, solution B is obtained；
1.3) solution A and solution B are mixed to get fluxing agent.
The temperature of described drying and processing is 40～100 DEG C, and the time of drying and processing is 20～40s.
Beneficial effects of the present invention is embodied in:
The present invention is at zinc chloride, ammonium chloride, stannous chloride and hexamethylenamine aqueous solution add and comprises ethanol, nonionic surfactant and the compound surfactant of cationic surfactant, can make to have between fluxing agent and steel piece good wettability and the compatibility, improve activity and the utilization rate of fluxing agent, fluxing agent is conducive to form one layer of uniform salt film on steel piece surface, thus improve steel piece, such as surface of steel plate activity, reduce the surface tension of alloy solution, prevent through oil removing, the clean steel iron piece surface second oxidation that rust cleaning obtains, thus can improve and help plating effect, prevent plating leakage, reduce cadmia to produce, prevent plating solution from splashing, improve quality of coating.
By experimental results demonstrate: the use of fluxing agent of the present invention can effectively prevent plating leakage, and makes the surface quality of coating be obviously improved, and the yield rate of plating piece is brought up to 99% by 36%, and the corrosion resisting property of coating is significantly improved.
Without environmentally harmful fluorion in fluxing agent of the present invention, meet environment protection requirement, and preparation cost is relatively low.Meanwhile, compound surfactant has low bubble, water solublity, when preparing fluxing agent, only need to be stirred at room temperature uniformly by compound surfactant and other component of fluxing agent, simple to operate, and solves multicomponent solutions and once prepare and easily precipitate'sProblem.
Accompanying drawing explanation
Figure 1For carrying out acid salt spray test 0h steel disc coating surface signal with reference to GB6459-86Figure；
Figure 2Illustrate for steel disc corrosion of coating situation after carrying out acid salt spray test 240h with reference to GB6459-86Figure。
Detailed description of the invention
Below in conjunction withAccompanying drawingWith embodiment, the present invention is elaborated.
The special fluxing agent being applicable to thermal dip plating of steel zinc-aluminium nickel rare earth alloy coating that the present invention uses is by two kinds of solution compositions of A and B, and forming steps is as follows:
Step one, first weigh a certain amount of ammonium chloride, zinc chloride, stannous chloride, hexamethylenamine with electronic balance, being placed in the glass beaker of 500mL, being slowly added to deionized water and by magnetic stirrer until being completely dissolved；The indissoluble impurity in solution is fallen subsequently with the strainer filtering of 40～100 mesh；Add distilled water with glue head dropper in beaker, be settled to 500mL, more slowly solution is drained in the volumetric flask of 1L with Glass rod, finally according to standard, solution is settled to 1L；Now prepare standard solution A.
Step 2, the first respectively ethanol of measured amounts, nonionic surfactant and cationic surfactant, being placed in the glass beaker of 500mL, being slowly added to deionized water and by magnetic stirrer until being completely dissolved, without lamination；Subsequently this prepared solution glue head dropper is settled to 500mL, more slowly solution is drained in the volumetric flask of 1L with Glass rod, finally according to standard, solution is settled to 1L；Now prepare without layering and the standard solution B of low foam.
Two kinds of standard solution of A, B of step 3, respectively measured amounts are placed in the glass beaker of 500mL, are configured to the fluxing agent of certain volume.
Hot-dip experiment is as follows:
1) plating is helped: be positioned over by the beaker being contained with fluxing agent in the water-bath of constant temperature 40 DEG C, until fluxing agent temperature reaches 40 DEG C in beaker；Secondly (steel disc each surface uniform contact solution) in beaker is put into by processing (pickling and washing are mainly rust cleaning and remove iron and steel surface of test piece oxide layer) clean steel disc through oil removing, pickling and washing；It is slowly withdrawn steel disc after putting into about 30s；
2) steel disc of taking-up is quickly placed in 100 DEG C of drying ovens drying 20～40s；
3) finally the steel disc of drying is put into the melted zinc-aluminium nickel rare-earth alloy molten solution zinc-aluminium nickel rare-earth alloy molten solution based on zinc of 450～500 degrees Celsius (alloy solution refer to) and carries out hot-dip experiment.
Experimental example 1
Take zinc chloride 20g, ammonium chloride 15g, stannous chloride 6g, hexamethylenamine 0.1g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 25g, nonionic surfactant (NP-10) 0.80g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 1g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL and add to equipped with in the 500mL beaker of 200mL solution A, fully
Stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 10g/L, the ammonia chloride of 7.5g/L, the stannous chloride of 3g/L, the hexamethylenamine of 0.05g/L, the ethanol of 12.5g/L, the nonionic surfactant of 0.40g/L, the cationic surfactant of 0.50g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, there is plating leakage phenomenon in steel disc overlay coating, and coating surface is uneven and rough.
Experimental example 2
Take zinc chloride 30g, ammonium chloride 25g, stannous chloride 15g, hexamethylenamine 0.1g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 50g, nonionic surfactant (NP-10) 1g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 1.50g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 15g/L, the ammonia chloride of 12.5g/L, the stannous chloride of 7.5g/L, the hexamethylenamine of 0.05g/L, the ethanol of 25g/L, the nonionic surfactant of 0.50g/L, the cationic surfactant of 0.75g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is the most smooth.
Experimental example 3
Take zinc chloride 45g, ammonium chloride 30g, stannous chloride 20g, hexamethylenamine 0.2g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 80g, nonionic surfactant (NP-10) 1.40g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 2g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 22.5g/L, the ammonia chloride of 15g/L, the stannous chloride of 10g/L, the hexamethylenamine of 0.1g/L, the ethanol of 40g/L, the nonionic surfactant of 0.70g/L, the cationic surfactant of 1g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is the most smooth.
Experimental example 4
Take zinc chloride 60g, ammonium chloride 40g, stannous chloride 25g, hexamethylenamine 0.3g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 100g, nonionic surfactant (NP-10) 1.80g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 3g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 30g/L, the ammonia chloride of 20g/L, the stannous chloride of 12.5g/L, the hexamethylenamine of 0.15g/L, the ethanol of 50g/L, the nonionic surfactant of 0.90g/L, the cationic surfactant of 1.50g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is uniform and smooth.
Experimental example 5
Take zinc chloride 68g, ammonium chloride 45g, stannous chloride 30g, hexamethylenamine 0.3g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 130g, nonionic surfactant (NP-10) 2g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 3.50g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 34g/L, the ammonia chloride of 22.5g/L, the stannous chloride of 15g/L, the hexamethylenamine of 0.15g/L, the ethanol of 65g/L, the nonionic surfactant of 1g/L, the cationic surfactant of 1.75g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is uniform and smooth.
Experimental example 6
Take zinc chloride 75g, ammonium chloride 50g, stannous chloride 35g, hexamethylenamine 0.4g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 150g, nonionic surfactant (NP-10) 2.40g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 4g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 37.5g/L, the ammonia chloride of 25g/L, the stannous chloride of 17.5g/L, the hexamethylenamine of 0.2g/L, the ethanol of 75g/L, the nonionic surfactant of 1.20g/L, the cationic surfactant of 2g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is uniform and smooth.
Experimental example 7
Take zinc chloride 90g, ammonium chloride 60g, stannous chloride 40g, hexamethylenamine 0.5g；Solution A is strictly prepared by above-mentioned steps one；Take ethanol 200g, nonionic surfactant (NP-10) 3g, cationic surfactant (myristyl benzyl dimethyl ammonium chloride) 5g respectively；B solution (built reactive agent) is strictly prepared by above-mentioned steps two；
Take built reactive agent 200mL to add to equipped with in the 500mL beaker of 200mL solution A, stir prepared experiment fluxing agent；This fluxing agent formula is: the zinc chloride of 45g/L, the ammonia chloride of 30g/L, the stannous chloride of 20g/L, the hexamethylenamine of 0.25g/L, the ethanol of 100g/L, the nonionic surfactant of 1.50g/L, the cationic surfactant of 2.50g/L, and remaining is deionized water.
Testing through hot-dip, after using this fluxing agent, steel disc overlay coating quality is good, plating leakage phenomenon does not occur, and coating surface is uniform and smooth.
The hot dip zinc-aluminium nickel rare earth alloy steel plate prepared by experimental example 1～7 carries out acid salt spray test, with 240h as experimental period, experimental result with reference to GB6459-86Such as table 1Shown in:
Table 1. acid salt fog result of the test
| Coating morphology | Average corrosion rate (g.m-2h-1) | |
| Experimental example 1 | Rough | 0.3662 |
| Experimental example 2 | More smooth | 0.3255 |
| Experimental example 3 | More smooth | 0.3051 |
| Experimental example 4 | Smooth | 0.2685 |
| Experimental example 5 | Smooth | 0.2237 |
| Experimental example 6 | Smooth | 0.2034 |
| Experimental example 7 | Smooth | 0.1953 |
In the formula of above-mentioned experiment, in experimental example 7, steel disc quality of coating and corrosion resistance are substantially better than other steel disc coating.SeeFigure 1AndFigure 2, it can be seen that experimental example 7 galvanizing rear surface smooth (Figure 1), 240 hours acid salt spray test rear surfaces do not have obvious red rust (Figure 2)。
The invention provides a kind of special fluxing agent being applicable to thermal dip plating of steel zinc-aluminium nickel rare earth alloy coating, built reactive agent is as additive, purpose is to make have more preferable interface wet ability between fluxing agent and product, improve fluxing agent activity and utilization rate, make quality of coating be obviously improved, and the corrosion resisting property of coating is improved significantly.But being as built reactive agent and add excess, coating surface quality improves inconspicuous, and corrosion resistance improves the most inconspicuous.
Fluxing agent of the present invention has good ingredient stability, the iron oxide film of surface of steel plate residual can be effectively peeled off, improve surface of steel plate activity, reduce the surface tension of alloy solution, improve the aluminium alloy wellability to steel matrix, prevent through oil removing, the clean steel board substrate surface obtained of eliminating rust by secondary oxidation, and fluxing agent of the present invention not fluoride ion, environmentally safe.
Claims (7)
1. a hot-dip aluminum zinc nickel rare earth alloy fluxing agent, it is characterised in that: this fluxing agent include with
The stannous chloride of lower component: the ammonia chloride of zinc chloride, 12.5～50g/L, 7.5～the 40g/L of 10～70g/L,
The non-ionic surface of the ethanol of hexamethylenamine, 25～150g/L, 0.50～the 2.40g/L of 0.05～0.4g/L is lived
Property agent and the cationic surfactant of 0.75～7g/L.
The most according to claim 1, a kind of hot-dip aluminum zinc nickel rare earth alloy fluxing agent, its feature exists
In: described fluxing agent include following components: zinc chloride, 20～the 50g/L of 10～70g/L ammonia chloride,
The ethanol of the hexamethylenamine of stannous chloride, 0.1～0.4g/L, 25～the 150g/L of 10～40g/L,
The nonionic surfactant of 0.80～2.40g/L and the cationic surfactant of 0.80～5g/L.
The most according to claim 1, a kind of hot-dip aluminum zinc nickel rare earth alloy fluxing agent, its feature exists
In: described fluxing agent be by water and zinc chloride, ammonium chloride, stannous chloride, ethanol, hexamethylenamine,
Nonionic surfactant and the formulated aqueous solution of cationic surfactant.
The most according to claim 1, a kind of hot-dip aluminum zinc nickel rare earth alloy fluxing agent, its feature exists
In: described nonionic surfactant is selected from alkylphenol polyoxyethylene, described cationic surfactant
Selected from quaternary cationics.
5. a hot-dip aluminum zinc nickel rare earth alloy technology method, it is characterised in that: comprise the following steps:
1) preparation fluxing agent
Described fluxing agent is made up of water and the following components that is dissolved in the water: the zinc chloride of 10～70g/L,
The hexamethylenamine of the stannous chloride of ammonia chloride, 7.5～40g/L, 0.05～the 0.4g/L of 12.5～50g/L,
The nonionic surfactant of ethanol, 0.50～the 2.40g/L of 25～150g/L and the sun of 0.75～7g/L from
Sub-surface activating agent；
2) steel piece that will be clean immerses in fluxing agent and carry out helping plating, described in help the temperature of plating
Being 40～60 DEG C, the time helping plating is 20～50s, dries the steel piece after helping plating
Process, make the uniform fluxing agent film of steel piece surface attachment one layer, then immerse melted zinc-aluminium nickel rare earth conjunction
Gold liquid carries out hot-dip.
The most according to claim 5, a kind of hot-dip aluminum zinc nickel rare earth alloy technology method, its feature exists
In described step 1) specifically include following steps:
1.1) by ammonium chloride, zinc chloride, stannous chloride and hexamethylenamine water dissolution, solution A is obtained；
1.2) by ethanol, nonionic surfactant and cationic surfactant water dissolution, obtain molten
Liquid B；
1.3) solution A and solution B are mixed to get fluxing agent.
The most according to claim 5, a kind of hot-dip aluminum zinc nickel rare earth alloy technology method, its feature exists
In: the temperature of described drying and processing is 40～100 DEG C, and the time of drying and processing is 20～40s.
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| CN106801208A (en) * | 2016-12-22 | 2017-06-06 | 当涂县宏宇金属炉料有限责任公司 | A kind of steel fluxing agent |
| CN107699833A (en) * | 2017-08-16 | 2018-02-16 | 江苏飞拓界面工程科技有限公司 | Help plating additive, quickening liquid and hot dip coating method |
| CN107937851A (en) * | 2017-11-08 | 2018-04-20 | 天津正天医疗器械有限公司 | New and effective structural member hot dip Galfan fluxing agents and preparation method and application |
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