CN112553556A - Production process of aluminum-zinc-magnesium alloy plating solution and aluminum-zinc-magnesium alloy plating layer - Google Patents
Production process of aluminum-zinc-magnesium alloy plating solution and aluminum-zinc-magnesium alloy plating layer Download PDFInfo
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- -1 aluminum-zinc-magnesium Chemical compound 0.000 title claims abstract description 163
- 238000007747 plating Methods 0.000 title claims abstract description 138
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 170
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 155
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 98
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 96
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 238000001816 cooling Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 125
- 239000007788 liquid Substances 0.000 claims description 35
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- 238000004090 dissolution Methods 0.000 claims description 27
- 229910000831 Steel Inorganic materials 0.000 claims description 25
- 239000010959 steel Substances 0.000 claims description 25
- 229910018571 Al—Zn—Mg Inorganic materials 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 abstract description 42
- 229910017706 MgZn Inorganic materials 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 11
- 229910017708 MgZn2 Inorganic materials 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 206010027146 Melanoderma Diseases 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003618 dip coating Methods 0.000 abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 description 44
- 238000012360 testing method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 229910019805 Mg2Zn11 Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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Classifications
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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
- C23C2/12—Aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- 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
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application relates to the technical field of hot dip coating materials, and particularly discloses a production process of an aluminum-zinc-magnesium alloy plating solution and an aluminum-zinc-magnesium alloy coating. The process comprises the following steps: adding nano aluminum oxide particles into the ammonium chloride solution, mixing, and cooling to form an ammonium chloride block containing aluminum oxide; adding the ammonium chloride block into the aluminum melt, uniformly mixing, and pouring to form aluminum balls containing aluminum oxide; the aluminum-zinc-magnesium raw melt is uniformly added into a container in which aluminum balls are piled, the aluminum balls are submerged and overflow out of the container, the aluminum balls are melted and flow out together with the aluminum-zinc-magnesium raw melt in the container to form a first mixed meltAnd then mixing the aluminum-zinc-magnesium alloy plating solution with the aluminum-zinc-magnesium raw solution overflowing from the container to form the aluminum-zinc-magnesium alloy plating solution containing nano aluminum oxide particles. The production process reduces the formation of Zn + Al + MgZn in the process of forming a coating by cooling the aluminum-zinc-magnesium alloy plating solution2The requirement of ternary eutectic structure, and all formed Zn + Al + MgZn2The ternary eutectic structure improves the corrosion resistance of the coating, and the coating has no black spot defect and uniform crystal patterns.
Description
Technical Field
The application relates to the technical field of hot dip coating materials, in particular to a production process of an aluminum-zinc-magnesium alloy plating solution.
Background
The surface of steel products such as steel strips, pipes, wires and the like is usually subjected to an anti-corrosion treatment to increase the use effect and the service life of the steel products. The aluminum-zinc-magnesium plating solution is used as a better anti-corrosion material and is widely applied to the surface anti-corrosion treatment of steel products.
During the cooling solidification process, a ternary eutectic structure is formed in the aluminum-zinc-magnesium coating. However, the aluminum-zinc-magnesium plating solution contains more components, which easily causes the formation of a complex and different ternary eutectic structure. It has been demonstrated that the ternary eutectic structure comprises Zn + Al + MgZn2Ternary eutectic structure and Zn + Al + Mg2Zn11Ternary eutectic structures are two main types. Wherein, Zn + Al + MgZn2The corrosion resistance of the coating can be improved by the ternary eutectic structure, but Zn + Al + Mg2Zn11The ternary eutectic structure easily causes the coating to have black spot defects and seriously influences the corrosion resistance of the coating. Therefore, how to form ternary eutectic structures beneficial to the product weight by controlling the crystallization process is a key to the technology.
In the related art, the method of controlling the post-plating cooling of the aluminum-zinc-magnesium plating solution after hot-dipping the aluminum-zinc-magnesium plating solution, that is, increasing the post-plating cooling rate to increase the supercooling degree of the crystal, is usually adopted, so as to obtain Zn + Al + MgZn2A ternary eutectic structure.
However, the cooling rate after plating is required to be controlled accurately in the related art, and the plating solution on the steel product and the surface thereof needs to be cooled synchronously to form a plating layer. After the thick steel product is subjected to hot dip plating treatment, the thick steel product has very high heat and is difficult to cool in a short time, and after the hot dip plating solution is subjected to hot dip plating, the difficulty of quickly cooling down the plating solution on the surface of the steel product is high; after the thin steel product is subjected to hot dip plating treatment, the temperature of the thin steel product is easy to lower, after the steel product is subjected to hot dip plating, the plating solution on the surface of the steel product and the plating solution on the surface of the steel product are difficult to control within a proper temperature range for cooling at the same time, and the corrosion resistance of the obtained steel or the steel product after plating is poor due to too high cooling speed. Therefore, the product with the aluminum-zinc-magnesium coating produced by adopting the technology for controlling the cooling speed after plating in the related technology has low qualification rate of only 60-80 percent, a large amount of unqualified products can only be degraded for use, and the economic benefit is seriously influenced.
Content of application
In order to reduce the formation of Zn + Al + MgZn during the cooling process for forming the aluminum-zinc-magnesium coating2The requirement of ternary eutectic structure, and all formed Zn + Al + MgZn2Ternary eutectic structure, difficult to form Zn + Al + Mg2Zn11A ternary eutectic structure, the application provides a production process of an aluminum-zinc-magnesium alloy plating solution and an aluminum-zinc-magnesium alloy plating layer.
On one hand, the production process of the aluminum-zinc-magnesium alloy plating solution provided by the application adopts the following technical scheme:
a production process of an aluminum-zinc-magnesium alloy plating solution comprises the following steps:
firstly, melting ammonium chloride to form ammonium chloride solution, adding nano aluminum oxide particles into the ammonium chloride solution, fully mixing, and cooling to form an ammonium chloride block containing the nano aluminum oxide particles;
step two, melting aluminum to form aluminum melt, adding the ammonium chloride block containing the nano aluminum oxide particles obtained in the step one into the aluminum melt, uniformly mixing, and pouring to form aluminum balls containing the nano aluminum oxide particles; melting the aluminum-zinc-magnesium alloy to obtain an aluminum-zinc-magnesium raw solution, intensively stacking the aluminum balls containing the nano aluminum oxide particles in a container made of refractory materials, and then melting and mixing the aluminum balls containing the nano aluminum oxide particles by using the aluminum-zinc-magnesium raw solution to form an aluminum-zinc-magnesium alloy plating solution containing the nano aluminum oxide particles;
the melting and mixing treatment comprises the following steps: uniformly adding the aluminum-zinc-magnesium raw melt into a container stacked with aluminum balls containing nano aluminum oxide particles, enabling the aluminum balls to submerge the aluminum balls containing the nano aluminum oxide particles and overflow out of the container, dispersing the nano aluminum oxide particles in the aluminum balls into the aluminum-zinc-magnesium raw melt in the container, and enabling the nano aluminum oxide particles to flow out together to form a first mixed melt; mixing the first mixed solution with the aluminum-zinc-magnesium raw solution overflowing from the container to form an aluminum-zinc-magnesium alloy plating solution containing nano aluminum oxide particles;
the weight ratio of the aluminum-zinc-magnesium raw melt liquid to the first mixed melt liquid of the overflow container is 1 (8-10.1);
in the first step, the particle size of the nano aluminum oxide particles is 200-400 nm.
Through the technical scheme, in the first step, the nano aluminum oxide particles are added into the ammonium chloride solution, and the ammonium chloride wraps the nano aluminum oxide particles to reduce the attraction among the nano aluminum oxide particles, so that the nano aluminum oxide particles are favorably and fully dispersed to form the ammonium chloride block containing the nano aluminum oxide particles.
And in the second step, adding the ammonium chloride block into the aluminum melt, gasifying the ammonium chloride at high temperature to mix the aluminum melt with the nano aluminum oxide particles, wherein the nano aluminum oxide particles can be uniformly dispersed in the aluminum melt, the aluminum balls obtained after casting can be kept in a uniformly distributed state, and the gasified ammonium chloride can also play a role in purifying the aluminum melt.
In the third step, the aluminum ball is not oxidized due to the contact of the aluminum ball with air by the aluminum zinc magnesium raw solution passing through the aluminum ball, and the aluminum ball is fully melted (the melting is called as melting because the aluminum zinc magnesium raw solution is used as a solvent, and the aluminum ball is placed in the aluminum ball, so that the aluminum ball is melted, the nano aluminum oxide particles are fully dispersed and mixed with the aluminum zinc magnesium raw solution), and the first mixed solution which flows out uniformly contains the nano aluminum oxide particles and is uniformly mixed with the aluminum zinc magnesium raw solution which overflows from the container.
Through the steps, the nano aluminum oxide particles can be fully suspended and dispersed in the aluminum-zinc-magnesium alloy plating solution, wherein the two reasons are as follows:
on one hand, the grain diameter of the nano aluminum oxide particles is within the range of 200-400nm, the nano aluminum oxide particles are uniformly dispersed in the aluminum-zinc-magnesium alloy plating solution, and Zn + Al + MgZn can be completely formed in the crystallized aluminum-zinc-magnesium alloy plating layer after the nano aluminum oxide particles are plated on the surface of a steel product2Ternary eutectic structure, thereby improving the anti-corrosion capability of the coating.
If the particle size of the nano aluminum oxide particles is less than 200nm, the core cannot be formed easily, and Zn + Al + MgZn cannot be promoted easily2Forming a ternary eutectic structure; if the grain diameter of the nano aluminum oxide particles is more than 400nm, the short-range order in the aluminum-zinc-magnesium plating solution can not form nuclei on the nano aluminum oxide particles to grow, and can not be crystallized into Zn + Al + MgZn on the nano aluminum oxide particles2The ternary eutectic structure causes the nanometer aluminum oxide particles to lose the function as the crystallization cores and instead become an impurity existing in the aluminum-zinc-magnesium alloy plating solution.
On the other hand, the weight ratio of the aluminum-zinc-magnesium raw melt overflowing the container to the first mixed melt is 1 (8-10.1), and under the condition of the weight ratio, the nano aluminum oxide particles are favorably suspended in the formed aluminum-zinc-magnesium alloy plating solution uniformly.
According to the technical scheme, the nano aluminum oxide particles are equivalently added into the aluminum-zinc-magnesium raw solution, and the nano aluminum oxide particles meet the suspension and dispersion conditions in the obtained aluminum-zinc-magnesium alloy plating solution and become Zn + Al + MgZn due to the characteristics of nano size, high melting point, particles, surface tension, specific gravity and the like2Ternary eutectic organization core conditions.
After the steel product is hot-dipped in the aluminum-zinc-magnesium alloy plating solution in which the nano aluminum oxide particles are uniformly dispersed, the aluminum-zinc-magnesium alloy plating solution on the surface of the steel product has no strict requirement on cooling, the cooling speed does not need to be controlled particularly, namely the cooling speed does not need to be controlled within a specific process range, and the nano aluminum oxide particles can be used for cooling according to the self-limited conditions of equipment used for a plating layer product in the process of forming the plating layerThe particles are taken as cores and all form Zn + Al + MgZn2Ternary eutectic structure without Zn + Al + Mg2Zn11The ternary eutectic structure, and the crystal grain of the formed ternary eutectic structure is fine, compact and regularly distributed, thereby improving the anti-corrosion capability of the plating layer and greatly reducing the cost for forming the plating layer by cooling after hot dip coating.
Preferably, in the first step, the weight of the nano aluminum oxide particles accounts for 20-40% of the weight of the nano aluminum oxide particles and the ammonium chloride solution.
Through the technical scheme, when the weight ratio of the nano aluminum oxide particles is in the range, the nano aluminum oxide particles are fully dispersed by the ammonium chloride solution at reasonable cost.
Preferably, the size of the ammonium chloride block containing nano aluminum oxide particles obtained in the first step is 20-100 mm.
Through the technical scheme, after the ammonium chloride block is contacted with the aluminum melt, the nano aluminum oxide particles can be fully dispersed in the aluminum melt in a short time. If the size of the ammonium chloride block is less than 20mm, the ammonium chloride block is mixed with the aluminum melt to cause the gasification speed of the ammonium chloride block to be too high, so that the nano aluminum oxide particles cannot be uniformly suspended in the aluminum melt; if the size of the ammonium chloride block is larger than 100mm, the gasification speed of the ammonium chloride block is easy to be too slow, so that the time required for the nano aluminum oxide particles to be fully dispersed in the aluminum melt is longer.
Preferably, in the second step, the weight of the ammonium chloride block containing the nano aluminum oxide particles accounts for 10-20% of the total weight of the ammonium chloride block containing the nano aluminum oxide particles and the aluminum melt.
By the technical scheme, when the weight ratio of the ammonium chloride block containing the nano aluminum oxide particles is within the range of 10-20%, the ammonium chloride is favorably gasified sufficiently, so that the nano aluminum oxide particles in the ammonium chloride block are uniformly dispersed and suspended in the aluminum melt.
Preferably, the particle size of the aluminum ball containing the nano aluminum oxide particles obtained in the second step is 30-100 mm.
Through the technical scheme, in the process of melting the aluminum balls by the aluminum-zinc-magnesium raw solution, the particle size of the aluminum balls containing the nano aluminum oxide particles is in the range, so that the nano aluminum oxide particles and the aluminum-zinc-magnesium raw solution are favorably and fully mixed, and the production progress of the aluminum-zinc-magnesium alloy plating solution is relatively fast.
If the particle size of the aluminum balls is less than 30mm, the aluminum balls are easy to melt at an excessively high speed, and the nano aluminum oxide particles in the aluminum balls cannot be fully dispersed; if the particle size of the aluminum ball is larger than 100mm, the melting speed of the aluminum ball is too low, and the mixing time of the aluminum-zinc-magnesium raw solution and the nano aluminum oxide particles is influenced, namely the production progress of the aluminum-zinc-magnesium alloy plating solution is influenced.
Preferably, in the third step, the container is a mixer, a dissolving chamber for containing aluminum balls containing nano aluminum oxide particles is arranged in the mixer, a tapered liquid outlet with a large upper part and a small lower part which is communicated with the dissolving chamber is arranged at the bottom of the mixer, a dissolving chamber bottom with honeycomb holes distributed on the end surface is arranged between the dissolving chamber and the liquid outlet, and a dissolving chamber cover with honeycomb holes distributed on the end surface is detachably arranged between the dissolving chamber and the overflow groove; the top of the mixer is provided with an overflow groove communicated with the dissolving chamber; the height of the dissolving chamber cover is lower than the overflow height of the overflow groove, and the overflow groove is communicated with the overflow groove.
Through above-mentioned technical scheme, nanometer aluminium oxide granule is arranged in the dissolving chamber steadily, and the honeycomb holes on the dissolving chamber lid are convenient for the former melt of aluminium zinc magnesium to flow in, and the overflow launder is convenient for the former melt overflow of unnecessary aluminium zinc magnesium to flow out, and the honeycomb holes at the bottom of the dissolving chamber, the fluid outflow is convenient for at the liquid outlet.
Preferably, the melting and mixing process comprises the steps of:
s1, placing the bottom of the dissolving chamber at the bottom of the dissolving chamber, intensively stacking the aluminum balls containing the nano aluminum oxide particles in the dissolving chamber, and placing the cover of the dissolving chamber at the bottom of the overflow groove;
s2, uniformly adding the aluminum-zinc-magnesium raw melt into the overflow groove, enabling the aluminum-zinc-magnesium raw melt to enter the dissolving chamber through the honeycomb holes on the dissolving chamber cover and keeping the dissolving chamber in a full state, melting aluminum balls containing nano aluminum oxide particles and forming a first mixed melt with the aluminum-zinc-magnesium raw melt, enabling the first mixed melt to flow out of the liquid outlet, meanwhile, enabling the aluminum-zinc-magnesium raw melt to overflow from the overflow port on the overflow groove and converging with the first mixed melt to form the aluminum-zinc-magnesium alloy plating solution containing the nano aluminum oxide particles.
Through the technical scheme, the bottom of the dissolving chamber and the cover of the dissolving chamber are placed, and the aluminum balls containing the nano aluminum oxide particles are stably stacked in the dissolving chamber. When the aluminum-zinc-magnesium original solution is added into the overflow groove and flows into the dissolving chamber, the aluminum ball containing the nano aluminum oxide particles is not covered, so that the aluminum ball can be fully dissolved, and the nano aluminum oxide particles contained in the aluminum ball are mixed with the aluminum-zinc-magnesium original solution and the melted aluminum solution together, so that the aluminum-zinc-magnesium alloy plating solution is fully suspended in the formed aluminum-zinc-magnesium alloy plating solution.
Preferably, the pore diameter of the honeycomb holes in the dissolving chamber cover and the dissolving chamber bottom is 5-25 mm; the total area of the honeycomb holes of the dissolving chamber cover is 1.1-2.0 times of the total area of the honeycomb holes of the dissolving chamber bottom.
Through above-mentioned technical scheme, the structure that the velocity of flow is greater than the velocity of flow below above forming, can accomplish the packing to dissolving the room, discharge the air, be favorable to the former melt of aluminium zinc magnesium to get into dissolving the room through honeycomb holes and contact and with its submergence with aluminium ball wherein, dissolve the aluminium ball, make its and former melt of aluminium zinc magnesium, nanometer aluminium oxide granule flow together, and the aperture scope is reasonable, be difficult for causing the aluminium ball not yet dissolved just to be taken out from the honeycomb holes at the bottom of the dissolving room.
Preferably, the diameter of the lower end of the liquid outlet is 50-150mm, the cone angle of the liquid outlet is 5-25 degrees, and the total area of the honeycomb holes at the bottom of the dissolving chamber is 1.1-2.0 times of the minimum area of the lower end of the liquid outlet.
Through the technical scheme, the flow velocity of the aluminum balls is further increased from top to bottom, the aluminum balls are fully melted, and the phenomenon that the aluminum balls flow out along with the aluminum-zinc-magnesium raw melt without being melted is avoided.
On the other hand, the aluminum-zinc-magnesium alloy coating provided by the application adopts the following technical scheme:
an aluminum-zinc-magnesium alloy coating is obtained by hot dipping a steel product into an aluminum-zinc-magnesium alloy plating solution and then cooling; in the aluminum-zinc-magnesium alloy coating, the weight of the nano aluminum oxide particles accounts for 0.0005-0.005% of the total weight of the aluminum-zinc-magnesium alloy coating.
By adopting the technical scheme, the steel product can be cooled after being hot-dipped with the aluminum zinc magnesium alloy plating solution to obtain the alloy containing more Zn, Al and MgZn2The coating with a ternary eutectic structure, wherein the weight ratio of the nano aluminum oxide particles is 0.0005-0.005%, so that the aluminum-zinc-magnesium alloy coating has better anti-corrosion performance.
In summary, the present application has the following beneficial effects:
1. treating the nano aluminum oxide particles by ammonium chloride solution to enable the nano aluminum oxide particles to be uniformly suspended in the ammonium chloride solution, and cooling to form ammonium chloride small blocks containing the nano aluminum oxide particles; and adding the small ammonium chloride blocks into the aluminum melt, gasifying the ammonium chloride, and after pouring and cooling, forming aluminum balls containing nano aluminum oxide particles, so that the nano aluminum oxide particles are uniformly distributed in the aluminum balls containing the nano aluminum oxide particles. Further, the aluminum-zinc-magnesium raw solution is uniformly added to the stacked aluminum balls containing the nano aluminum oxide particles, so that the aluminum balls are uniformly dissolved, the nano aluminum oxide particles are uniformly mixed with the aluminum solution and the aluminum-zinc-magnesium raw solution to form the aluminum-zinc-magnesium plating solution, and the nano aluminum oxide particles are uniformly suspended in the aluminum-zinc-magnesium plating solution in a particle form.
2. Adding nano aluminum oxide particles into the aluminum-zinc-magnesium raw solution to form an aluminum-zinc-magnesium alloy plating solution in which the nano aluminum oxide particles are uniformly dispersed, wherein the nano aluminum oxide particles exist as cores of heterogeneous nuclei, the steel product is hot-dipped, the aluminum-zinc-magnesium alloy plating solution on the surface of the steel product does not need to control the cooling speed particularly, namely the cooling speed does not need to be controlled in a specific process window, and a large amount of Zn + Al + MgZn can be formed by taking the nano aluminum oxide particles as the cores in the process of forming a plating layer2The ternary eutectic structure has no black point defect, and the formed ternary eutectic structure has fine and compact crystal grains and regular distribution, thereby improving the corrosion resistance of the coatingCapability.
3. The particle size of the nano aluminum oxide particles, the size of the ammonium chloride small blocks containing the nano aluminum oxide particles and the particle size of the aluminum balls containing the nano aluminum oxide particles are respectively limited in range, so that the nano aluminum oxide particles are more favorably and uniformly distributed in the finally obtained aluminum-zinc-magnesium alloy plating solution.
4. In the aluminum-zinc-magnesium alloy coating, the weight of the nano aluminum oxide particles accounts for 0.0005-0.005% of the total weight of the aluminum-zinc-magnesium alloy coating, which is favorable for controlling the grain size of the obtained aluminum-zinc-magnesium alloy coating within 3-5mm, the grain size is uniform and consistent, and the grain size is similar to that of a diamond, commonly called as 'diamond grain flower', so that the obtained aluminum-zinc-magnesium alloy coating has a better appearance effect.
Drawings
FIG. 1 is a schematic structural view of the present embodiment;
FIG. 2 is a side sectional view of the mixer of the present embodiment;
FIG. 3 is a cross-sectional view A-A of FIG. 2;
fig. 4 is a schematic view of a disassembly structure of the mixer in this embodiment.
In the figure, 100, a main plating pot; 200. a premelting pot; 300. a launder; 400. a mixer; 410. an overflow trough; 411. an overflow port; 420. a dissolution chamber; 430. a liquid outlet; 600. a dissolution chamber cover; 700. and (4) dissolving the chamber bottom.
Detailed Description
The present application is described in further detail below.
Embodiment 1 a production process of an aluminum-zinc-magnesium alloy plating solution, comprising the following steps:
firstly, melting ammonium chloride to form ammonium chloride solution, adding 300nm nanometer aluminum oxide particles with the particle size of 200-;
step two, melting aluminum to form aluminum melt, adding the ammonium chloride block containing the nano aluminum oxide particles obtained in the step one into the aluminum melt, uniformly mixing the ammonium chloride block containing the nano aluminum oxide particles and the aluminum melt, and pouring to form aluminum balls containing the nano aluminum oxide particles with the particle size of 30-50mm, wherein the weight of the added ammonium chloride block containing the nano aluminum oxide particles accounts for 10% of the total weight of the ammonium chloride block containing the nano aluminum oxide particles and the aluminum melt;
and step three, melting the aluminum-zinc-magnesium alloy to obtain an aluminum-zinc-magnesium raw melt, wherein the components and the content of the components in the aluminum-zinc-magnesium raw melt are shown in the table 1, and then melting and mixing the components in a mixer.
Wherein, referring to fig. 2 and fig. 3, a dissolving chamber 420 for accommodating aluminum balls containing nano aluminum oxide particles is arranged in the mixer 400, a tapered liquid outlet 430 with a large top and a small bottom is arranged at the bottom of the mixer 400 and communicated with the dissolving chamber 420, a dissolving chamber bottom 700 with honeycomb holes distributed on the end surface is arranged between the dissolving chamber 420 and the liquid outlet 430, a dissolving chamber cover 600 with honeycomb holes distributed on the end surface is detachably arranged between the dissolving chamber 420 and the overflow groove 410, referring to fig. 3 and fig. 4, the dissolving chamber cover 600 is connected through a bolt, and the aperture of each honeycomb hole is 5 mm. Wherein the total area of the honeycomb holes of the dissolution chamber cover 600 is 1.1 times the total area of the honeycomb holes of the dissolution chamber bottom 700.
Referring to fig. 2 and 3, an overflow tank 410 communicating with a dissolution chamber 420 is provided at the top of the mixer 400. The dissolving chamber cover 600 is lower than the overflow height of the overflow groove 410, the overflow groove 300 is communicated with the overflow groove 410, and an overflow port 411 is arranged on one side of the overflow groove 410 far away from the overflow groove 300.
Referring to fig. 1 and 2, one end of the mixer 400 is connected with a chute 300 which is inclined upwards, and one end of the chute 300, which is far away from the mixer 400, is connected with a premelting pot 200, the upper end of the chute 300 is communicated with the inner wall of the premelting pot 200, the premelting pot 200 is used for melting and storing the aluminum-zinc-magnesium raw melt, and the aluminum-zinc-magnesium raw melt flows into the mixer 400 through the chute 300; and the liquid outlet 430 of the mixer 400 extends into the main plating pot 100. And the diameter of the lower end of the liquid outlet 430 is 50mm, and the taper angle of the liquid outlet 430 is 5 °. And the total area of the honeycomb holes of the dissolution chamber bottom 700 is 2.0 times the minimum area of the lower end of the liquid outlet 430.
And the launder 300, the main plating pot 100, the pre-melting pot 200, the mixer 400, the dissolving chamber cover 600 and the dissolving chamber bottom 700 are all made of refractory castable (meeting the requirements of any one of the trade standards YB/T5083-2014 high-alumina castable on the brands of GLJ-65, GLJ-70 and GLJ-80).
The specific dissolving and mixing treatment in the third step comprises the following steps:
s1, placing the bottom 700 of the dissolving chamber at the bottom of the dissolving chamber 420, intensively stacking the aluminum balls containing the nano aluminum oxide particles in the dissolving chamber, and placing the cover 600 of the dissolving chamber at the bottom of the overflow groove 410;
s2, adding an aluminum-zinc-magnesium alloy ingot into the pre-melting pot 200, melting the ingot into a raw aluminum-zinc-magnesium solution at 598 ℃, allowing the raw aluminum-zinc-magnesium solution to flow into the upper part of the dissolution chamber cover 600 through the launder 300, allowing the raw aluminum-zinc-magnesium solution to enter the dissolution chamber 420 through the honeycomb holes in the dissolution chamber cover 600, keeping the dissolution chamber 420 in a full state, immersing the aluminum balls, allowing the aluminum balls containing nano aluminum oxide particles to be melted and form a first mixed solution with the raw aluminum-zinc-magnesium solution, allowing the first mixed solution to flow out from the liquid outlet 430, and allowing part of the raw aluminum-zinc-magnesium solution to overflow from the overflow launder 410 and to be merged with the first mixed solution in the main plating pot 100 to form the aluminum-zinc-magnesium plating solution. And the weight ratio of the raw aluminum-zinc-magnesium melt overflowing from the overflow launder 410 to the first mixed melt is 1: 9.
Wherein, the weight of the nano aluminum oxide particles accounts for 0.0005 percent of the total weight of the aluminum-zinc-magnesium alloy coating.
Examples 2 to 3 a process for producing an aluminum-zinc-magnesium alloy plating bath, which is different from example 1 in the contents of Al, Mg, Si, Zn components in the aluminum-zinc-magnesium alloy, wherein the kinds and contents of inevitable impurities are almost the same.
TABLE 1 concrete components and contents thereof contained in the Al-Zn-Mg alloys of examples 1 to 3
Embodiment 4. a production process of an aluminum-zinc-magnesium alloy plating solution, which is different from embodiment 1 in that in the step one, the particle size of the adopted nano aluminum oxide particles is 250-350 nm.
Embodiment 5 a production process of an aluminum-zinc-magnesium alloy plating solution, which is different from embodiment 1 in that in the step one, the particle size of the adopted nano aluminum oxide particles is 300-400 nm.
Embodiment 6A production process of an Al-Zn-Mg alloy plating solution, which is different from embodiment 1 in that, in the step one, the weight of the added nano aluminum oxide particles accounts for 28% of the total weight of the nano aluminum oxide particles and the ammonium chloride solution.
Embodiment 7 is a process for producing an aluminum-zinc-magnesium alloy plating solution, which is different from embodiment 1 in that in the first step, the ratio of the weight of the added nano aluminum oxide particles to the total weight of the nano aluminum oxide particles and the ammonium chloride solution is 40%.
Embodiment 8 a process for producing an aluminum-zinc-magnesium alloy plating solution, which is different from embodiment 1 in that the size of the ammonium chloride lumps containing nano aluminum oxide particles formed in the step one is 40 to 60 mm.
Example 9 a process for producing an al-zn-mg alloy plating bath, which is different from example 1 in that the size of the ammonium chloride cake containing nano-alumina particles formed in the first step is 50 to 100 mm.
Embodiment 10 a process for producing an al-zn-mg alloy plating solution, which is different from embodiment 1 in that, in the second step, the weight of the added ammonium chloride blocks containing nano-alumina particles accounts for 15% of the total weight of the ammonium chloride blocks containing nano-alumina particles and the aluminum melt.
Embodiment 11 a process for producing an al-zn-mg alloy plating solution, which is different from embodiment 1 in that, in the second step, the weight of the ammonium chloride blocks containing nano-alumina particles added is 20% of the total weight of the ammonium chloride blocks containing nano-alumina particles and the aluminum melt.
Embodiment 12 a process for producing an al-zn-mg alloy plating bath, which is different from embodiment 1 in that, in the second step, aluminum balls containing nano alumina particles having a particle size of 50 to 80mm are formed after casting.
Embodiment 13 a process for producing an al-zn-mg alloy plating bath, which is different from embodiment 1 in that in the second step, aluminum balls containing nano aluminum oxide particles with a particle size of 81-100mm are formed after casting.
Example 14A production process of an Al-Zn-Mg alloy plating bath, which is different from example 1 in that in the third step, the diameters of honeycomb holes in the dissolution chamber cover 600 and the dissolution chamber bottom 700 in the mixer 400 are both 15mm, and the total area of the honeycomb holes of the dissolution chamber cover 600 is 1.2 times that of the honeycomb holes of the dissolution chamber bottom 700; the diameter of the lower end of the liquid outlet 430 is 100mm, the taper angle of the liquid outlet 430 is 15 °, and the total area of the honeycomb holes of the dissolution chamber bottom 700 is 2.0 times the minimum area of the lower end of the liquid outlet 430.
Example 15A production process of an Al-Zn-Mg alloy plating bath, which is different from example 1 in that in the third step, the diameters of honeycomb holes in the dissolution chamber cover 600 and the dissolution chamber bottom 700 in the mixer 400 are both 25mm, and the total area of the honeycomb holes of the dissolution chamber cover 600 is 1.3 times that of the honeycomb holes of the dissolution chamber bottom 700; the diameter of the lower end of the liquid outlet 430 is 150mm, the taper angle of the liquid outlet 430 is 25 °, and the total area of the honeycomb holes of the dissolution chamber bottom 700 is 1.1 times the minimum area of the lower end of the liquid outlet 430.
Example 16A process for producing an aluminum-zinc-magnesium alloy plating bath, which is different from example 1 in that the weight ratio of the raw aluminum-zinc-magnesium melt overflowing from the overflow vessel 410 to the first mixed melt is 1: 8.
Example 17A process for producing an aluminum-zinc-magnesium alloy plating bath, which is different from example 1 in that the weight ratio of the raw aluminum-zinc-magnesium melt overflowing from the overflow vessel 410 to the first mixed melt is 1: 10.1.
Embodiment 18 a process for producing an al-zn-mg alloy plating solution, which is different from embodiment 1 in that the nano-alumina particles account for 0.001% by weight of the total weight of the al-zn-mg alloy plating layer.
Example 19A process for producing an Al-Zn-Mg alloy plating bath, which is different from example 1, wherein the nano-alumina particles account for 0.003% of the total weight of the Al-Zn-Mg alloy plating layer.
Example 20A process for producing an Al-Zn-Mg alloy plating bath, which is different from example 1 in that the nano-alumina particles account for 0.005% by weight of the total weight of the Al-Zn-Mg alloy plating layer.
Examples 21 to 40: an aluminum-zinc-magnesium alloy coating is prepared by the following preparation process:
step A, carrying out degreasing, rinsing, drying and continuous annealing treatment on a rolled hard carbon steel plate (the thickness is 0.8mm +/-0.02 mm);
and step B, respectively hot dipping the treated steel plates in the aluminum-zinc-magnesium alloy plating solution prepared in the embodiment 1-17 at 598 ℃, passing through the aluminum-zinc-magnesium alloy plating solution at the speed of 150m/min, blowing off the redundant plating solution by an air knife, and then cooling to form an aluminum-zinc-magnesium alloy plating layer on the surfaces of the steel plates.
Comparative example 1 a process for producing an al-zn-mg plating solution, which is different from example 1 in that nano-alumina particles are replaced with equal weight of magnesium oxide (available from yoto aochu chemical ltd).
Comparative example 2 a process for producing an al-zn-mg plating solution, which is different from example 1 in that nano-alumina particles were replaced with zinc oxide (purchased from south river, shou chemical limited) in an equal weight.
Comparative example 3: a production process of an aluminum-zinc-magnesium plating solution is different from that of comparative example 1 in that magnesium oxide is added to a raw aluminum-zinc-magnesium solution and mixed at a speed of 300rpm for 1 hour in the process of preparing the aluminum-zinc-magnesium plating solution.
Comparative example 4: a production process of an aluminum-zinc-magnesium plating solution differs from that of comparative example 2 in that zinc oxide is added to a raw aluminum-zinc-magnesium solution and mixed at a speed of 300rpm for 1 hour in the preparation of the aluminum-zinc-magnesium plating solution.
Comparative example 5 a process for producing an aluminum-zinc-magnesium plating solution, which is different from example 1 in that 5% of aluminum, 0.2% of magnesium and the balance of zinc are added together into a melting furnace and melted by heating to form a plating solution.
Comparative example 6A production process of a plating solution, which is different from the production process of the example 1, is characterized in that an aluminum zinc silicon solution is used for replacing an aluminum zinc magnesium raw solution, and the production process comprises the following components in percentage by weight: 55% of Al, 1.6% of Si and the balance of Zn.
Comparative example 7. a production process of a zinc-aluminum-magnesium plating solution, which is different from the example 1 in that an aluminum-zinc-magnesium alloy consists of the following components in percentage by weight: 25% of Al, 1.5% of Mg, 0.8% of Si and the balance of Zn.
Comparative example 8 a process for producing an aluminum-zinc-magnesium plating solution, which is different from example 1, comprises the steps of:
a1, adding nano aluminum oxide particles with the particle size of 200-400nm into the aluminum melt, uniformly mixing, and pouring to form aluminum balls containing the nano aluminum oxide particles;
a2, uniformly adding the raw aluminum-zinc-magnesium melt into the overflow tank, allowing the raw aluminum-zinc-magnesium melt to enter the dissolution chamber through the honeycomb holes on the dissolution chamber cover 600 and keeping the dissolution chamber in a full state, melting the aluminum balls containing nano aluminum oxide particles and forming a mixed melt A with the raw aluminum-zinc-magnesium melt, allowing the mixed melt A to flow out of the liquid outlet 430, and simultaneously allowing the raw aluminum-zinc-magnesium melt to overflow from the overflow tank 410 and join with the mixed melt A to form an aluminum-zinc-magnesium plating solution A, which is usually placed in the main plating pot 100.
Comparative examples 9 to 17: an aluminum-zinc-magnesium coating is prepared by the following preparation process:
step A, degreasing, rinsing, drying and continuously annealing a CR4 grade cold-rolled carbon steel plate (the thickness is 0.8mm +/-0.02 mm) meeting ISO 3574;
and step B, respectively hot dipping the cold-rolled carbon steel plate in the plating solution prepared in the comparative examples 1 to 8, passing through the plating solution at the speed of 200m/min, taking out, cooling and forming a corresponding plating layer on the surface of the cold-rolled carbon steel plate.
Testing and detecting:
test one: examples 21 to 40 were used as test samples 1 to 20, and comparative examples 9 to 17 were used as control samples 1 to 9; respectively carrying out plating layer thickness tests on the test samples 1-20 and the comparison samples 1-9 by adopting a Tianrui Thick800A plating layer thickness tester; respectively analyzing the coating structures of the test sample 1-20 and the reference sample 1-9 by an X-ray diffractometer (XRD) to determine whether Zn + Al + Mg exist in the coating2Zn11And (4) carrying out ternary eutectic structure and visual inspection to determine whether black spot defects exist, and recording and analyzing results.
And (2) test II: according to GB/T10125-.
And (3) test results: table 2 shows the results of the test samples 1 to 20 and the control samples 1 to 9.
TABLE 2 summary of the conditions of test samples 1-20 and control samples 1-9
As can be seen from Table 2, in the test samples 1 to 20, the weight ratio of the nano aluminum oxide particles to the total weight of the aluminum-zinc-magnesium alloy and the nano aluminum oxide particles was in the range of 0.0005 to 0.005%, and the thickness of the formed plating layer was in the range of 2 to 30 μm, and Zn + Al + Mg was not present2Zn11Ternary eutectic structure and black point defects. This indicates that the test samples 1-20 all formed Zn + Al + MgZn during the conventional cooling solidification process2The ternary eutectic structure also shows that by adopting the production process in the application, not only does the requirement of rapid cooling or specific cooling conditions not need to be adopted, but also Zn + Al + MgZn can be completely formed in the formed coating under the conventional cooling conditions2Ternary eutectic structure without generating Zn + Al + Mg2Zn11The diameter of the crystal flower is 2-3mm, 3-4mm and 4-5mm, the size is uniform, the distribution of the crystal flower is uniform, the anti-corrosion effect of the coating is improved, and the anti-corrosion capability of each test sample is 4000 hours or even more than 5000 hours under the condition of neutral salt spray.
In the test samples 14-15, the cell diameter, the diameter of the lower end of the liquid outlet, the taper angle of the liquid outlet, and the total area of the bottom of the dissolution chamber were multiples of the minimum area of the lower end of the liquid outletAll varied, but the thickness of the finally obtained coating, the diameter of the spangles, whether black spot defects exist, whether Zn + Al + Mg exists or not2Zn11Indexes such as ternary eutectic structures are similar to those of other test samples, and the indexes show that the full dispersion of nano aluminum oxide particles can be realized by adopting the mixer adopted in the application and matching with parameter ranges of various structures, and Zn + Al + MgZn is formed in the coating2A ternary eutectic structure.
In the test samples 18 to 20, the distribution of the nano-alumina particles as cores in the coating is more compact due to the increased content of the nano-alumina particles in the coating, and thus, Zn + Al + MgZn formed by using the nano-alumina particles as cores2The distribution of the ternary eutectic structure is uniform and more compact, so that the plating layer achieves better corrosion resistance.
In the comparison samples 1-4, magnesium oxide and zinc oxide are respectively adopted to replace nano aluminum oxide particles, but finally, corresponding aluminum-zinc-magnesium alloy plating solutions which are fully mixed are difficult to form, and finally, the plating solution with Zn + Al + MgZn is difficult to form2Coating of ternary eutectic structure, resulting in Zn + Al + Mg2Zn11The three-element eutectic structure causes black point defects, and the sizes of the crystal flowers are different and the distribution is uneven. And in the neutral salt spray test process, the formed product can not be detected. Compared with the test samples 1-20, the nano aluminum oxide particles can be fully matched with the aluminum-zinc-magnesium raw solution only by adopting the nano aluminum oxide particles, and uniformly distributed Zn + Al + MgZn are formed in the coating formed after cooling2A ternary eutectic structure.
In the control sample 5, the Al-Zn-Mg raw melt is directly used for hot dip coating, wherein the content of Mg is extremely low, so that Zn + Al + MgZn is not generated2Ternary eutectic structure, and no Zn + Al + Mg2Zn11Ternary eutectic structures and black point defects, but the corrosion prevention effect can only reach 2760h under a neutral salt spray test, which shows that the corrosion prevention effect of a coating formed by the plating solution is poorer than that of the test samples 1-20.
In control 6, the aluminum-zinc-silicon melt was used for hot dip coating, and the formed coating was less likely to come outNow Zn + Al + MgZn2Ternary eutectic structure and Zn + Al + Mg2Zn11And the corrosion resistance of the coating is poorer than that of the test samples 1-20 although the crystal flower size and distribution are relatively uniform.
In control 7, the Al-Zn-Mg raw melt contains different components and corresponding contents, which results in easy formation of Zn + Al + Mg2Zn11The ternary eutectic structure has a black spot defect, although crystal flowers appear, the crystal flowers have different sizes and overlarge sizes, and the distribution of the crystal flowers is seriously uneven, so that the corrosion resistance in the comparison sample 7 is poor.
The phenomena in the control samples 5-7 were caused by the different contents and main components of the aluminum-zinc-magnesium melt, which means that Zn + Al + MgZn was formed in the coating2The ternary eutectic structure is also critical to the selection of the aluminum-zinc-magnesium alloy with different component contents.
In comparative sample 8, the thickness of the plating layer was thick and a certain amount of Zn + Al + Mg was present2Zn11Ternary eutectic structures and black point defects, sizes of crystal flowers are different, the crystal flowers are not uniformly distributed, and different crystals are formed in the cooling process. Compared with the test samples 1-20, the phenomenon is caused because the nano aluminum oxide particles are difficult to be fully dispersed in the formation process of the aluminum-zinc-magnesium alloy plating solution of the comparison sample 8, the thickness of the formed plating layer is larger, the nano aluminum oxide particles which are not fully dispersed are agglomerated, and finally, in the process of forming the plating layer by cooling, the black spot defect is caused and even is accompanied with certain Zn + Al + Mg2Zn11A ternary eutectic structure appears. Therefore, the production process adopted in the application is needed to fully disperse the nano aluminum oxide particles in the obtained aluminum-zinc-magnesium alloy plating solution, and finally, the full dispersion can be formed in the plating layer, so that compact and uniform Zn + Al + MgZn is formed2A ternary eutectic structure.
In addition, the corresponding plating layers could be formed only under the condition of the corresponding cooling rates in the control samples 1 to 8, but the above cooling rates were respectively adopted in the test samples 1 to 22, but in the practical process, it was found that the corresponding plating layers could be formed at any temperature within the range of 2 to 10 ℃/min, which indicates that the process for preparing the test samples 1 to 22, i.e., the cooling rates in the operation processes of the examples 1 to 22, had little influence on the characteristics of the corresponding plating layers formed.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A production process of an aluminum-zinc-magnesium alloy plating solution is characterized by comprising the following steps:
firstly, melting ammonium chloride to form ammonium chloride solution, adding nano aluminum oxide particles into the ammonium chloride solution, fully mixing, and cooling to form an ammonium chloride block containing the nano aluminum oxide particles;
step two, melting aluminum to form aluminum melt, adding the ammonium chloride block containing the nano aluminum oxide particles obtained in the step one into the aluminum melt, uniformly mixing, and pouring to form aluminum balls containing the nano aluminum oxide particles;
melting the aluminum-zinc-magnesium alloy to obtain an aluminum-zinc-magnesium raw solution, intensively stacking the aluminum balls containing the nano aluminum oxide particles in a container made of refractory materials, and then melting and mixing the aluminum balls containing the nano aluminum oxide particles by using the aluminum-zinc-magnesium raw solution to form an aluminum-zinc-magnesium alloy plating solution containing the nano aluminum oxide particles;
the melting and mixing treatment comprises the following steps: uniformly adding the aluminum-zinc-magnesium raw melt into a container stacked with aluminum balls containing nano aluminum oxide particles, enabling the aluminum balls to submerge the aluminum balls containing the nano aluminum oxide particles and overflow out of the container, dispersing the nano aluminum oxide particles in the aluminum balls into the aluminum-zinc-magnesium raw melt in the container, and enabling the nano aluminum oxide particles to flow out together to form a first mixed melt; mixing the first mixed solution with the aluminum-zinc-magnesium raw solution overflowing from the container to form an aluminum-zinc-magnesium alloy plating solution containing nano aluminum oxide particles;
the weight ratio of the aluminum-zinc-magnesium raw melt liquid to the first mixed melt liquid of the overflow container is 1 (8-10.1);
in the first step, the particle size of the nano aluminum oxide particles is 200-400 nm.
2. The production process of an Al-Zn-Mg alloy plating solution as claimed in claim 1, wherein in the first step, the ratio of the weight of the nano alumina particles to the total weight of the nano alumina particles and the ammonium chloride solution is 20-40%.
3. The process for producing an aluminum-zinc-magnesium alloy plating solution according to claim 1, wherein the size of the ammonium chloride block containing nano aluminum oxide particles obtained in the first step is 20-100 mm.
4. The process for producing an Al-Zn-Mg alloy plating solution according to claim 1, wherein in the second step, the weight of the ammonium chloride blocks containing nano aluminum oxide particles accounts for 10-20% of the total weight of the ammonium chloride blocks containing nano aluminum oxide particles and the aluminum melt.
5. The production process of the aluminum-zinc-magnesium alloy plating solution as recited in claim 1, wherein the aluminum ball containing the nano-alumina particles obtained in the second step has a particle size of 30 to 100 mm.
6. The production process of an aluminum-zinc-magnesium alloy plating solution according to any one of claims 1 to 5, characterized in that in the third step, the container is a mixer (400), a dissolving chamber (420) for containing aluminum balls containing nano aluminum oxide particles is arranged in the mixer (400), a tapered liquid outlet (430) with a large upper part and a small lower part is arranged at the bottom of the mixer (400) and communicated with the dissolving chamber (420), a dissolving chamber bottom (700) with honeycomb holes distributed on the end surface is arranged between the dissolving chamber (420) and the liquid outlet (430), and a dissolving chamber cover (600) with honeycomb holes distributed on the end surface is detachably arranged between the dissolving chamber (420) and the overflow tank (410); an overflow groove (410) communicated with the dissolving chamber (420) is arranged at the top of the mixer (400); the height of the dissolving chamber cover (600) is lower than the overflow height of the overflow groove (410), and the overflow groove (300) is communicated with the overflow groove (410).
7. The process for producing an aluminum-zinc-magnesium alloy plating solution according to any one of claim 6, wherein the melting and mixing treatment comprises the steps of:
s1, placing the bottom (700) of the dissolving chamber at the bottom of the dissolving chamber (420), intensively stacking the aluminum balls containing the nano aluminum oxide particles in the dissolving chamber (420), and placing the cover (600) of the dissolving chamber at the bottom of the overflow groove (410);
s2, uniformly adding the aluminum-zinc-magnesium raw melt into the overflow groove (410), enabling the aluminum-zinc-magnesium raw melt to enter the dissolving chamber (420) through the honeycomb holes on the dissolving chamber cover (600) and keeping the dissolving chamber (420) in a full state, melting aluminum balls containing nano aluminum oxide particles and forming a first mixed melt with the aluminum-zinc-magnesium raw melt, enabling the first mixed melt to flow out of the liquid outlet (430), meanwhile, enabling the aluminum-zinc-magnesium raw melt to overflow from an overflow port (411) on the overflow groove (410) and join with the first mixed melt to form the aluminum-zinc-magnesium alloy plating solution containing the nano aluminum oxide particles.
8. The production process of an Al-Zn-Mg alloy plating solution as claimed in claim 7, wherein the honeycomb holes in the dissolution chamber cover (600) and the dissolution chamber bottom (700) have a pore size of 5-25 mm; the total area of the honeycomb holes of the dissolving chamber cover (600) is 1.1-2.0 times of the total area of the honeycomb holes of the dissolving chamber bottom (700).
9. The process for producing an Al-Zn-Mg alloy plating solution according to claim 7, characterized in that the diameter of the lower end of the liquid outlet (430) is 50-150mm, the cone angle of the liquid outlet (430) is 5-25 °, and the total area of the honeycomb holes of the dissolution chamber bottom (700) is 1.1-2.0 times the minimum area of the lower end of the liquid outlet (430).
10. An Al-Zn-Mg alloy plating layer, which is characterized in that the Al-Zn-Mg alloy plating layer is obtained by hot dipping a steel product into the Al-Zn-Mg alloy plating solution of any one of the claims 1 to 9 and then cooling; in the aluminum-zinc-magnesium alloy coating, the weight of the nano aluminum oxide particles accounts for 0.0005-0.005% of the total weight of the aluminum-zinc-magnesium alloy coating.
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| CN103507324A (en) * | 2012-06-20 | 2014-01-15 | 鞍钢股份有限公司 | Alloyed zinc aluminum magnesium alloy coated steel plate and production method thereof |
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| CN106868394A (en) * | 2016-12-26 | 2017-06-20 | 安徽宝恒新材料科技有限公司 | A kind of method for improving steel plate mechanical performance |
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| US20200354580A1 (en) * | 2019-05-09 | 2020-11-12 | Zirconia Inc. | Protective coatings for galvanized steel |
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| CN111519121A (en) * | 2020-04-15 | 2020-08-11 | 马鞍山钢铁股份有限公司 | Method for reducing hot galvanizing zinc steam |
| CN111826598A (en) * | 2020-07-28 | 2020-10-27 | 攀钢集团研究院有限公司 | Wear-resistant corrosion-resistant zinc-aluminum-magnesium coated steel plate and preparation method thereof |
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