CN116254538A - Zinc-aluminum-magnesium steel and preparation process thereof - Google Patents
Zinc-aluminum-magnesium steel and preparation process thereof Download PDFInfo
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- CN116254538A CN116254538A CN202310218896.XA CN202310218896A CN116254538A CN 116254538 A CN116254538 A CN 116254538A CN 202310218896 A CN202310218896 A CN 202310218896A CN 116254538 A CN116254538 A CN 116254538A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 28
- -1 Zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000004907 flux Effects 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 229910000677 High-carbon steel Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 106
- 238000007747 plating Methods 0.000 claims description 78
- 229910052742 iron Inorganic materials 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007716 flux method Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005246 galvanizing Methods 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013980 iron oxide Nutrition 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 229910000861 Mg alloy Inorganic materials 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 239000011833 salt mixture Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 3
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
-
- 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
-
- 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
- C23C2/26—After-treatment
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/081—Iron or steel solutions containing H2SO4
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention discloses a zinc-aluminum-magnesium steel and a preparation process thereof, wherein the zinc-aluminum-magnesium steel comprises the following materials: pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2. The MgCl2 in the flux has good covering effect and certain refining capability on the magnesium melt, is easy to mix with other salts to form a low-melting-point salt mixture, can be rapidly spread on the surface of the metal melt to form a continuous and tight flux layer, can well wet magnesium oxide on the surface of the melt, effectively adsorbs impurities suspended in the melt, can obviously reduce the melting point, surface tension and viscosity of MgCl2, reduces the evaporation loss of MgCl2 at high temperature, and can increase the density and viscosity of the flux by CaF2 and BaCl2, so that the flux and the zinc-magnesium alloy melt are easier to separate, and the appearance of a coating can be ensured to be smooth and bright.
Description
Technical Field
The invention relates to the field of preparation of zinc-aluminum-magnesium steel, in particular to zinc-aluminum-magnesium steel and a preparation process thereof.
Background
The zinc aluminum magnesium is alloy metal, is mainly used for surface corrosion prevention treatment of steel and iron products, comprises various zinc series plating layers and a large number of steel, the metal originally used for surface corrosion prevention treatment of the iron and steel products is pure zinc, along with the development of technology, the aluminum zinc alloy, zinc aluminum magnesium alloy and other alloy metals appear successively, the corrosion prevention effect of a metal layer is increased, more impurities are generated when the existing zinc aluminum magnesium steel is prepared, the precision of the product is easily influenced, meanwhile, the appearance of the zinc aluminum magnesium steel does not have a smooth and bright effect, the temperature cannot be well controlled when the hot dip galvanizing process is carried out, the surface finish of the obtained plating layer is poor, the thickness of the pure zinc layer is thick, and the consumption of zinc is also large.
Disclosure of Invention
The invention mainly aims to provide zinc-aluminum-magnesium steel and a preparation process thereof, which can effectively solve the problems in the background technology.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a zinc aluminum magnesium steel material comprising the following materials: pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2.
Preferably, the hydrochloric acid concentration is 36% -38%.
A preparation process of zinc-aluminum-magnesium steel, which comprises the following operation steps:
s1: preparing instruments and materials: the instrument comprises a crucible resistance furnace and a SIC crucible, wherein the materials comprise pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2;
s2: alkali washing: preparing NaOH, na2CO3 and Na3PO4 into a 20% solution according to the concentration of 1:1:1, heating alkali liquor to 70-80 ℃, removing greasy dirt on the surface of the pre-plating piece through the alkali liquor, and removing residual alkali liquor on the surface of the pre-plating piece through water washing after degreasing;
s3: acid washing: the scale and rust remaining on the surface of the sample are removed by acid washing, wherein three effects are included, including dissolution: the oxide of various iron in the iron scale on the surface of the sample reacts with acid to generate ferric salt dissolved in water and then dissolved in acid solution, when hydrochloric acid and sulfuric acid are used for pickling, normal iron, ferrous chloride and sulfate which are soluble in the acid solution are generated, so that the iron scale is removed from the surface of the strip steel, and the mechanical stripping effect is achieved: besides various oxides of iron removal, part of metal iron is mixed in the iron scale on the surface of the sample, and the iron scale has porosity, so that an acid solution can act with iron or matrix iron in the iron scale through pores and cracks of the iron scale, and a large amount of hydrogen is correspondingly generated, and the iron scale can be peeled off from the surface of the strip steel under the expansion pressure generated by the hydrogen, so that the reduction effect is realized: when metal iron reacts with acid, hydrogen atoms are firstly generated, part of the hydrogen atoms are mutually combined to form hydrogen molecules, so that iron scale is promoted to be stripped, and the other part of the hydrogen atoms reduce oxides of high-valence iron and high-valence ferric salt into low-valence iron oxides and low-valence ferric salt which are easily dissolved in acid solution by virtue of chemical activity and strong reducing capability;
s4: washing: washing the acid-washed material with water, and placing the washed material in a flusher for flushing until residual acid, ferric salt, residues and the like on the surface of the pre-plated piece are removed;
s5: flux treatment: the cleaned pre-plating piece is processed by flux as soon as possible, a small amount of oxide skin generated by oxidation in the air after the pre-plating piece is pickled is removed, ferric salt which is not completely pickled on the surface of the pre-plating piece and oxide on the surface of molten metal are removed, the surface tension of the molten metal is reduced, the surface of iron is promoted to wet the molten metal to create a clean and high-activity substrate surface, then the substrate surface is dried, and the pre-plating piece coated with a layer of dry flux is put into molten metal liquid for hot plating;
s6: hot dip plating: after passing the flux-treated pre-plated piece through plating solution, namely plating a layer of metal or alloy on the surface, wherein the flux-method hot dip plating requires external heating;
s7: and (3) cooling: the sample passing through the plating solution is placed in air or cooled in water.
Preferably, the heating mode of the flux method hot dip plating can adopt coal, heavy oil, coal gas or natural gas for heating, and meanwhile, a newly-built hot dip plating device can be adopted, and most of the hot dip plating devices can adopt resistance heating or induction heating.
Preferably, in the hot dip galvanizing, the temperature of the zinc liquid needs to be maintained between 445 and 455 ℃ in a low temperature range, and meanwhile, the hot dip temperature of ZN, AL and Mg needs to be between 500 and 550 ℃, and the hot dip time is within 10 to 30 seconds.
Preferably, the plating assistant agent to be put in needs to have the following adjustment: the minimum melting point and the minimum activity temperature of the flux component are lower than the melting point of the plating alloy, and the flux component has good infiltration performance with the matrix, so that the plating assistant can be in a liquid state to play a role in the dip plating process, can dissolve or remove solid oxide, protect the surface of the matrix from being oxidized, does not generate gas or emit gas, does not influence the quality of the plating layer, does not cause large variation of the components of the plating solution, and is easy to maintain the stability of the components of the plating solution.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, mgCl2 in the flux has good covering effect and certain refining capability on the magnesium melt, is easy to be mixed with other salts to form a low-melting-point salt mixture, can be rapidly spread into a continuous and tight flux layer on the surface of the metal melt, can well moisten magnesium oxide on the surface of the melt, effectively adsorbs impurities suspended in the melt, KCl can obviously reduce the melting point, surface tension and viscosity of MgCl2, reduces evaporation loss of MgCl2 at high temperature, caF2 and BaCl2 can increase the density and viscosity of the flux, so that the flux and the zinc magnesium alloy melt are easier to separate, and simultaneously can ensure that the appearance of a plating layer is smooth and bright, and in order to further prevent oxidation loss of Mg elements, a flux covering layer is also added in the hot plating process to protect the plating layer.
Description of the embodiments
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
First embodiment:
the invention relates to zinc-aluminum-magnesium steel, which comprises the following materials: pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2, and the plating auxiliary agents need to be adjusted as follows: the minimum melting point and the minimum activity temperature of the flux components are lower than the melting point of the plating alloy, and the flux components and the substrate have good infiltration performance, so that the plating assistant can be in a liquid state to play a role in the dip plating process, can dissolve or remove solid oxides, protect the surface of the substrate from being oxidized, avoid generating gas or releasing gas, avoid influencing the quality of the plating layer, avoid causing large variation of the components of the plating solution, and easily maintain the stability of the components of the plating solution, wherein the concentration of hydrochloric acid is 36-38%.
Specific embodiment II:
a preparation process of zinc-aluminum-magnesium steel comprises the following operation steps:
s1: preparing instruments and materials: the instrument comprises a crucible resistance furnace and a SIC crucible, and the materials comprise pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high-carbon steel, mgCl2, KCl, caF2 and BaCl2.
S2: alkali washing: preparing NaOH, na2CO3 and Na3PO4 into a 20% solution according to the concentration of 1:1:1, heating the alkali liquor to 70-80 ℃, removing greasy dirt on the surface of the pre-plating piece through the alkali liquor, and removing residual alkali liquor on the surface of the pre-plating piece through water washing after degreasing.
S3: acid washing: the scale and rust remaining on the surface of the sample are removed by acid washing, wherein three effects are included, including dissolution: the oxide of various iron in the iron scale on the surface of the sample reacts with acid to generate ferric salt dissolved in water and then dissolved in acid solution, when hydrochloric acid and sulfuric acid are used for pickling, normal iron, ferrous chloride and sulfate which are soluble in the acid solution are generated, so that the iron scale is removed from the surface of the strip steel, and the mechanical stripping effect is achieved: besides various oxides of iron removal, part of metal iron is mixed in the iron scale on the surface of the sample, and the iron scale has porosity, so that an acid solution can act with iron or matrix iron in the iron scale through pores and cracks of the iron scale, and a large amount of hydrogen is correspondingly generated, and the iron scale can be peeled off from the surface of the strip steel under the expansion pressure generated by the hydrogen, so that the reduction effect is realized: when the metallic iron reacts with acid, hydrogen atoms are generated first, part of the hydrogen atoms are mutually combined to form hydrogen molecules, so that the iron scale is promoted to be stripped, and the other part of the hydrogen atoms reduce the oxide of the high-valence iron and the high-valence ferric salt into the low-valence iron oxide and the low-valence ferric salt which are easy to dissolve in an acid solution by virtue of the chemical activity and the strong reducing capability of the hydrogen atoms.
S4: washing: and (3) washing the material subjected to acid washing, and placing the material in a flusher for flushing until residual acid, ferric salt, residues and the like on the surface of the pre-plated piece are removed.
S5: flux treatment: and (3) carrying out flux treatment on the cleaned pre-plated part as soon as possible, removing a small amount of oxide skin generated by oxidation of the pre-plated part in the air after pickling, removing ferric salt which is not completely pickled on the surface of the pre-plated part and oxide on the surface of molten metal, reducing the surface tension of the molten metal, promoting the surface of iron to wet the molten metal to create a clean and high-activity substrate surface, drying, and putting the pre-plated part coated with a layer of dry flux into molten metal liquid for hot plating.
S6: hot dip plating: after passing through plating solution, plating a layer of metal or alloy on the surface, wherein the flux method hot dip plating requires external heating, the flux method hot dip plating can adopt coal, heavy oil, gas or natural gas for heating, meanwhile, a newly built hot dip plating device can be adopted, the hot dip plating device can adopt resistance heating or induction heating, the temperature of the zinc solution needs to be maintained within 445-455 ℃ in the low temperature range during hot dip galvanizing, the hot dip plating temperature of ZN, AL and Mg needs to be 500-550 ℃, and the hot dip plating time is within 10-30 seconds.
S7: and (3) cooling: the sample passing through the plating solution is placed in air or cooled in water.
Third embodiment:
the prepared material is naturally dried for 0.5h to 1h before being cleaned, then the material is cleaned by clean flowing water with the temperature not higher than 40 ℃, and the air with the temperature not higher than 200kpa is used for blow-drying at the position 300mm away from the sample, so that a salt spray test is performed, corrosive solution is compressed into air spray, the sample is sprayed, the spray is wrapped on each surface of the sample as much as possible, the test can be continuously or circularly performed until the corrosion phenomenon of the sample occurs, then the corrosion time is recorded as the corrosion resistance of the sample, the longer the time is, the better the corrosion resistance of the sample is indicated, and therefore, the corrosion resistance prepared by the preparation method is better, and the salt spray test with longer time can be born.
The MgCl2 in the flux has good covering effect and certain refining capability on the magnesium solution, is easy to be mixed with other salts to form a low-melting-point salt mixture, can be rapidly spread into a layer of continuous and tight flux layer on the surface of the metal solution, can well moisten magnesium oxide on the surface of the solution, effectively adsorbs impurities suspended in the solution, KCl can obviously reduce the melting point, surface tension and viscosity of MgCl2, reduces evaporation loss of MgCl2 at high temperature, caF2 and BaCl2 can increase the density and viscosity of the flux, so that the flux and the zinc magnesium alloy solution are easier to separate, and simultaneously can ensure that the appearance of a plating layer is smooth and bright, and in order to further prevent oxidation loss of Mg elements, a flux covering layer is also added in the hot plating process to protect the plating layer, the plating layer by means of surface tension, a continuous and complete covering layer is formed on the surface of the solution, air is isolated, mg and O2O are prevented from reacting, oxidation and deslagging effects of Mg are prevented, the fused flux has good adsorption effect on non-metal impurities and evaporation loss of MgCl2 at high temperature, the temperature and good adsorption effect of the zinc alloy solution and the metal impurities are also greatly influenced by the factors such as the difference of the zinc atom thickness, the zinc alloy layer is greatly influenced in the plating layer thickness, and the zinc atom thickness is greatly influenced by the thermal plating layer thickness, and the zinc alloy coating is greatly-coated zinc atom density is greatly influenced by the thermal plating layer, and the zinc alloy layer is greatly-coated by the effect of the surface plating layer is coated by the effect of zinc alloy, and has good effect of zinc plating effect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A zinc aluminum magnesium steel, characterized in that: the material comprises the following materials: pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2.
2. A zinc aluminum magnesium steel product according to claim 1, wherein: the concentration of hydrochloric acid is 36% -38%.
3. The process for preparing zinc-aluminum-magnesium steel according to claim 1, wherein the process comprises the following steps: the method comprises the following operation steps:
s1: preparing instruments and materials: the instrument comprises a crucible resistance furnace and a SIC crucible, wherein the materials comprise pure Zn, pure A1, galvalume alloy, zn-5% Mg intermediate alloy, hydrochloric acid, NH4CI, znCl2, naOH, na2CO3, na3CO3, no. two auxiliary agents, no. six auxiliary agents, high carbon steel, mgCl2, KCl, caF2 and BaCl2;
s2: alkali washing: preparing NaOH, na2CO3 and Na3PO4 into a 20% solution according to the concentration of 1:1:1, heating alkali liquor to 70-80 ℃, removing greasy dirt on the surface of the pre-plating piece through the alkali liquor, and removing residual alkali liquor on the surface of the pre-plating piece through water washing after degreasing;
s3: acid washing: the scale and rust remaining on the surface of the sample are removed by acid washing, wherein three effects are included, including dissolution: the oxide of various iron in the iron scale on the surface of the sample reacts with acid to generate ferric salt dissolved in water and then dissolved in acid solution, when hydrochloric acid and sulfuric acid are used for pickling, normal iron, ferrous chloride and sulfate which are soluble in the acid solution are generated, so that the iron scale is removed from the surface of the strip steel, and the mechanical stripping effect is achieved: besides various oxides of iron removal, part of metal iron is mixed in the iron scale on the surface of the sample, and the iron scale has porosity, so that an acid solution can act with iron or matrix iron in the iron scale through pores and cracks of the iron scale, and a large amount of hydrogen is correspondingly generated, and the iron scale can be peeled off from the surface of the strip steel under the expansion pressure generated by the hydrogen, so that the reduction effect is realized: when metal iron reacts with acid, hydrogen atoms are firstly generated, part of the hydrogen atoms are mutually combined to form hydrogen molecules, so that iron scale is promoted to be stripped, and the other part of the hydrogen atoms reduce oxides of high-valence iron and high-valence ferric salt into low-valence iron oxides and low-valence ferric salt which are easily dissolved in acid solution by virtue of chemical activity and strong reducing capability;
s4: washing: washing the acid-washed material with water, and placing the washed material in a flusher for flushing until residual acid, ferric salt, residues and the like on the surface of the pre-plated piece are removed;
s5: flux treatment: the cleaned pre-plating piece is processed by flux as soon as possible, a small amount of oxide skin generated by oxidation in the air after the pre-plating piece is pickled is removed, ferric salt which is not completely pickled on the surface of the pre-plating piece and oxide on the surface of molten metal are removed, the surface tension of the molten metal is reduced, the surface of iron is promoted to wet the molten metal to create a clean and high-activity substrate surface, then the substrate surface is dried, and the pre-plating piece coated with a layer of dry flux is put into molten metal liquid for hot plating;
s6: hot dip plating: after passing the flux-treated pre-plated piece through plating solution, namely plating a layer of metal or alloy on the surface, wherein the flux-method hot dip plating requires external heating;
s7: and (3) cooling: the sample passing through the plating solution is placed in air or cooled in water.
4. The process for preparing zinc-aluminum-magnesium steel according to claim 1, wherein the process comprises the following steps: the flux method hot dip plating can be heated by coal, heavy oil, coal gas or natural gas, and meanwhile, a newly-built hot dip plating device can be adopted, and most of the hot dip plating devices can be heated by resistance heating or induction heating.
5. The zinc-aluminum-magnesium steel and the preparation process thereof according to claim 1, wherein the preparation process is characterized in that: when the hot dip galvanizing is performed, the temperature of the zinc liquid needs to be maintained between 445 and 455 ℃ in a low temperature range, meanwhile, the hot dip temperature of ZN, AL and Mg needs to be between 500 and 550 ℃, and the hot dip time is within 10 to 30 seconds.
6. The process for preparing zinc-aluminum-magnesium steel according to claim 1, wherein the process comprises the following steps: the plating assistant agent to be put into the process is required to have the following adjustment: the minimum melting point and the minimum activity temperature of the flux component are lower than the melting point of the plating alloy, and the flux component has good infiltration performance with the matrix, so that the plating assistant can be in a liquid state to play a role in the dip plating process, can dissolve or remove solid oxide, protect the surface of the matrix from being oxidized, does not generate gas or emit gas, does not influence the quality of the plating layer, does not cause large variation of the components of the plating solution, and is easy to maintain the stability of the components of the plating solution.
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CN104711502A (en) * | 2013-12-15 | 2015-06-17 | 河南省电力勘测设计院 | Corrosion-resistant Zn-Al-Mg rare earth alloy coating, preparation and hot dipping method thereof |
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CN105734479A (en) * | 2016-03-14 | 2016-07-06 | 靖江新舟合金材料有限公司 | Production method for aluminum, magnesium and zinc coated steel plate |
CN110218959A (en) * | 2019-05-07 | 2019-09-10 | 江苏东纲金属制品有限公司 | A kind of bridge cable high corrosion-resistant Zn90-Al10-Mg Alloy Coating Steel Wire |
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CN104711502A (en) * | 2013-12-15 | 2015-06-17 | 河南省电力勘测设计院 | Corrosion-resistant Zn-Al-Mg rare earth alloy coating, preparation and hot dipping method thereof |
KR20150073033A (en) * | 2013-12-20 | 2015-06-30 | 주식회사 포스코 | Galvanized hot rolled steel sheet having excellent coatibility and method for manufacturing the same |
CN105734479A (en) * | 2016-03-14 | 2016-07-06 | 靖江新舟合金材料有限公司 | Production method for aluminum, magnesium and zinc coated steel plate |
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