CN110241369B - Zinc-aluminum-nickel-tantalum alloy for hot dipping and hot galvanizing method - Google Patents
Zinc-aluminum-nickel-tantalum alloy for hot dipping and hot galvanizing method Download PDFInfo
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- CN110241369B CN110241369B CN201910440032.6A CN201910440032A CN110241369B CN 110241369 B CN110241369 B CN 110241369B CN 201910440032 A CN201910440032 A CN 201910440032A CN 110241369 B CN110241369 B CN 110241369B
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- 238000007598 dipping method Methods 0.000 title claims abstract description 54
- 229910001362 Ta alloys Inorganic materials 0.000 title claims abstract description 49
- -1 Zinc-aluminum-nickel-tantalum Chemical compound 0.000 title claims abstract description 48
- 238000005246 galvanizing Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 52
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000000956 alloy Substances 0.000 claims abstract description 45
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 38
- 239000010959 steel Substances 0.000 claims abstract description 38
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- 239000006004 Quartz sand Substances 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 35
- 229910052725 zinc Inorganic materials 0.000 abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002893 slag Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000002411 adverse Effects 0.000 abstract description 2
- 230000004075 alteration Effects 0.000 abstract description 2
- 229910000676 Si alloy Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 238000007747 plating Methods 0.000 description 30
- 238000005260 corrosion Methods 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 20
- 230000006872 improvement Effects 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- 229910000617 Mangalloy Inorganic materials 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium 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
- C23C2/04—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention provides a zinc-aluminum-nickel-tantalum alloy for hot dipping, which comprises 0.1-25.0wt% of Al, 0.01-2wt% of Ni, 0.01-0.5wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping. The zinc-aluminum-chromium-calcium-silicon alloy for hot dipping is suitable for hot dipping processes of various steel materials with complex components, can reduce or maintain the content of harmful impurity iron element in zinc liquid of a galvanizing pot in a lower range, reduce the amount of zinc slag generated by galvanizing, simultaneously reduce adverse effects of bottom slag generated by galvanizing and increase of the content of iron element to increase galvanizing slag, and has the advantages of thin alloy coating formed after hot dipping, uniform thickness, no chromatic aberration, no Sandlin effect, no redundant zinc nodules and excellent coating quality.
Description
Technical Field
The invention relates to the technical field of hot galvanizing, in particular to a zinc-aluminum-nickel-tantalum alloy for hot galvanizing and a hot galvanizing method.
Background
Zinc is used in large quantities as an anti-corrosion protective layer for steel. The dissolution rate of zinc is high because of the large potential difference between the steel and the zinc layer. In a humid environment, the galvanized steel sheet is easy to corrode, so that a white corrosion product is formed on the surface of the galvanized steel sheet or the galvanized steel sheet becomes grey dark, and the appearance quality and the coating corrosion resistance of the galvanized steel sheet are influenced.
With the rapid development of the industries such as communication, electric power, automobiles, ships, household appliances, buildings and the like, the demand of hot-dip galvanized alloy products is increasing year by year, and the requirements on the product quality are continuously improved. The principle of the hot galvanizing alloy is as follows: cleaning iron rust on the surface of the steel part by acid washing or atmosphere reduction, then soaking the steel part into zinc alloy liquid after solvent treatment and drying or directly soaking the steel part into the zinc alloy liquid; and reacting iron on the surface of the steel part with the molten zinc to form an alloy coating on the surface of the steel structural part. In order to reduce the cost, improve the corrosion resistance, the surface property and the good mechanical property of a hot galvanizing product, reduce the generation amount of bottom slag and reduce the effective zinc waste caused by salvaging the bottom slag, the hot galvanizing alloy technology presents a new development trend.
In the hot galvanizing alloy industry at home and abroad at present, the alloy coating with trace alloy elements is added, so that the alloy coating has good surface quality, excellent corrosion resistance, excellent bonding performance and excellent mechanical performance. However, with the improvement of the steel production process, the components of the steel are complex, and the change causes the traditional hot-dip galvanized alloy to have certain galvanizing quality problems, such as the phenomenon of over-thick coating, uneven thickness, sandelin effect, color difference and the like, and meanwhile, the produced bottom slag is more, and the bottom slag is salvaged for many times in the production process, so that more effective zinc is wasted. On the other hand, the structure of the plated part is complex and the shape is changeable, for example, a large pipe tower part is made of steel materials with high silicon and manganese contents, the structure is more complex than that of single angle steel, channel steel, plate materials, flat steel, steel pipes, different types of strip steel and the like, the structure influences the heat transfer of zinc plating and the flow of zinc liquid, influences the adhesion of a plating layer and puts higher requirements on hot galvanizing alloy. The pickling time of large steel parts and complex steel parts is long, and the pickling is partially over-pickled; the over-pickling brings more iron particles into the plating assistant solution and the zinc alloy solution, so that the impurity iron in the zinc alloy solution is increased in the galvanizing process, and more zinc slag is generated. Meanwhile, the structural member has high hot dip coating requirement, needs to prolong the galvanizing time, and mainly shows the quality problems of poor zinc bath heat transfer effect, poor zinc bath fluidity, excessive iron dissolution of steel parts into zinc alloy liquid, thicker coating thickness, chromatic aberration of the coating, poor coating adhesion, possible particle occurrence of the coating, non-bright and smooth coating, zinc slag increase and the like in the galvanizing process. In the prior art, the commonly used zinc alloy for hot dip galvanizing alloy mainly comprises Zn-Al alloy and Zn-Ni alloy, which can not be applied to the hot dip coating process of the steel surface with complex components and can not effectively solve the problem of zinc slag increase caused by too many iron particles entering the zinc alloy liquid. The hot dip plating is carried out for more than 3 minutes, because the thickness of the plating layer is increased by iron particles to be more than 200 mu m, the plating layer becomes brittle, the local adhesion force of a plated part is poor, and simultaneously, more bottom slag is generated, so that 3-5 percent of zinc is wasted and cannot be effectively utilized.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zinc-aluminum-nickel-tantalum alloy for hot dipping, which contains 0.1-25.0wt% of Al, 0.01-2wt% of Ni, 0.01-0.5wt% of Ta and the balance of Zn and inevitable impurities carried by zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping, and effectively solves the technical problems that the existing zinc alloy cannot be applied to hot dipping on the surface of a steel material with complex components and structures, iron particles in a zinc alloy liquid are increased, and a large amount of bottom slag is generated to cause zinc waste in the prior art.
The invention provides a zinc-aluminum-nickel-tantalum alloy for hot dipping, which contains 0.1-25.0wt% of Al, 0.01-2wt% of Ni, 0.01-0.5wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping.
As a further improvement of the invention, the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 0.1wt% of Al, 0.01wt% of Ni and 0.01wt% of Ta based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping, and the balance of Zn and inevitable impurities carried by the zinc alloy.
As a further improvement of the invention, the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 25.0wt% of Al, 0.01wt% of Ni, 0.01wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping.
As a further improvement of the invention, the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 0.1wt% of Al, 2wt% of Ni, 0.5wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping.
As a further improvement of the invention, the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 20.0wt% of Al, 2wt% of Ni, 0.5wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping.
In a further improvement of the invention, the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 15.0wt% of Al, 2wt% of Ni and 0.5wt% of Ta based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping, and the balance is Zn and inevitable impurities carried by the zinc alloy.
The invention further protects a hot galvanizing method, which comprises the steps of adding an inorganic additive into the molten zinc-aluminum-nickel-tantalum alloy liquid for hot galvanizing, uniformly stirring, placing the substrate to be galvanized into the molten alloy liquid, and forming a coating on the surface of the substrate to be galvanized.
As a further improvement of the invention, the substrate to be plated is one of a structural member, strip steel, angle steel, channel steel, plate material, flat steel, steel pipe and large pipe tower member.
As a further improvement of the invention, the alloy liquid temperature is higher than 570 ℃.
As a further improvement of the invention, the inorganic additive is composed of the following raw materials in parts by weight: 2-5 parts of ammonium chloride, 3-5 parts of nano zirconia, 1-3 parts of nano magnesia, 5-10 parts of quartz sand, 0.1-0.5 part of lanthanum nitrate, 0.1-0.2 part of cerium nitrate, 1-2 parts of sodium molybdate and 0.1-0.3 part of europium nitrate; the addition amount of the inorganic additive is 0.01-0.05g/kg.
The invention has the following beneficial effects:
the white rust resisting time of the invention adopting the zincate passivation zinc coating can reach more than 24h, and MoO on the surface layer of the metal passivation film 4 2- Can block Cl - The destruction of eroding anions enables the passive film to have cation selectivity, and the corrosion resistance of the galvanized passive film is improved; the silicate conversion film on the zinc coating resists corrosion because the inner part of the film layer is provided with negative charge SiO 3 2- Or SiO 2 Forming a protective film by the coordination of the micelle and the positively charged polymer; the rare earth metal oxide nano zirconia and nano magnesia can be used for preparing a rare earth conversion film on a metal material, and plays a role of a corrosion inhibitor in a coating, so that the corrosion resistance of the coating is improved, and a good corrosion prevention effect is achieved; the trace lanthanum nitrate and cerium nitrate have certain improvement effect on the passivation of zinc alloy, and a physical barrier formed by a compound of a passivation film cerium blocks oxygen and electrons from flowing to a cathode to inhibit a cathode reaction; the silicon dioxide modified silane solution is used for improving the mechanical property and the corrosion property of aluminum alloy and hot-dip galvanized plates; europium has excellent high-temperature oxidation resistance and corrosion resistance, and has excellent electrical properties. The inorganic additive forms a layer of passive film on the surface of the plating layer, effectively prevents the metal plating layer from being corroded, and is environment-friendly and non-toxic.
The zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention is suitable for steel materials with various complex components and complex shapes by properly selecting the types and the contents of all components in the zinc alloy, particularly adding a proper amount of Al, si, cr and Ca trace elements into a zinc bath, and can effectively control the over-rapid growth of a zinc-iron alloy layer in the hot dipping process and simultaneously reduce the alloy melting point, so that the alloy zinc bath formed after the zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention is melted has higher fluidity, the free layer of a plating layer is thinned, the corrosion resistance and the mechanical property of the alloy plating layer can be effectively improved, the thickness of the alloy plating layer is more uniform, the color difference is avoided, the Sandlin effect is avoided, redundant zinc nodules are avoided, the plating quality is higher, iron particles in a zinc alloy liquid are reduced, the generation of bottom slag is reduced, the zinc is saved, and the zinc plating cost is reduced.
Detailed Description
The technical solutions in 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 obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
The invention provides a zinc-aluminum-nickel-tantalum alloy for hot dipping, which comprises 0.1-25.0wt% of Al, 0.01-2wt% of Ni, 0.01-0.5wt% of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping.
The inventor of the invention discovers through a large number of experiments that the aluminum-nickel-tantalum alloy for hot dipping provided by the invention is suitable for steel materials with various complicated components and shapes by properly selecting the component types and the content of the zinc alloy, particularly adding a proper amount of Al, ni and Ta microelements into a zinc bath, can effectively control the over-fast growth of a zinc-iron alloy layer in the hot dipping process, and can also reduce the melting point of the alloy, so that the alloy zinc bath formed by melting the aluminum-nickel-tantalum alloy for hot dipping provided by the invention has higher fluidity, the free layer of a plating layer becomes thinner, the corrosion resistance and the mechanical property of the alloy plating layer can be effectively improved, the thickness of the alloy plating layer formed after hot dipping is more uniform, and the aluminum-nickel-tantalum alloy for hot dipping has no chromatism, no Sandlin effect, no redundant zinc nodules and higher plating layer quality.
In the zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention, through the synergistic effect of Al, ni and Ta, the zinc-aluminum-nickel-tantalum alloy for hot dipping has an obvious effect on the hot dipping Sanderlin effect of high-silicon high-manganese steel, the adverse effect of promoting the too fast growth of a zinc-iron alloy layer by a silicon-manganese element in steel is effectively inhibited, the hot dipping lasts for more than 3 minutes, a coating is uniform, the thickness can be controlled to be about 100 mu m, the coating has good toughness and the local adhesive force of a plated piece is good, and the problem of poor adhesive force of the coating of a large tubular tower piece with a complex structure is effectively solved.
As the common knowledge of the technicians in the field, the zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention also contains inevitable impurities, the impurities exist in the conventional content, and the invention has no special requirement.
Example 1
A zinc-aluminum-nickel-tantalum alloy S1 for hot dipping contains 8wt% of Al, 0.1wt% of Ni, 0.05wt% of Ta and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive comprises the following raw materials in parts by weight: 2 parts of ammonium chloride, 3 parts of nano zirconia, 1 part of nano magnesia, 5 parts of quartz sand, 0.1 part of lanthanum nitrate, 0.1 part of cerium nitrate, 1 part of sodium molybdate and 0.1 part of europium nitrate.
An inorganic additive was added to the molten Zn-Al-Ni-Ta alloy S1 alloy liquid for hot dipping of this example in an amount of 0.05g/kg. And after uniform stirring, the temperature of the alloy liquid is 585 ℃, and the steel pipe is hot-dipped for 1.5 minutes, so that the thickness of the formed coating is uniform.
Example 2
A zinc-aluminum-nickel-tantalum alloy S2 for hot dipping comprises 20wt% of Al, 0.5wt% of Ni, 0.1wt% of Ta and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive is prepared from the following raw materials in parts by weight: 5 parts of ammonium chloride, 5 parts of nano zirconia, 3 parts of nano magnesia, 10 parts of quartz sand, 0.5 part of lanthanum nitrate, 0.2 part of cerium nitrate, 2 parts of sodium molybdate and 0.3 part of europium nitrate.
An inorganic additive was added to the molten Zn-Al-Ni-Ta alloy S2 alloy solution for hot dipping of this example in an amount of 0.01g/kg. And after the uniform stirring, the temperature of the alloy liquid is 575 ℃, the strip steel is hot-dipped for 15 seconds, and the thickness of the formed plating layer is uniform.
Example 3
A zinc-aluminum-nickel-tantalum alloy S3 for hot dipping contains 0.1wt% of Al, 0.2wt% of Ni, 0.1wt% of Ta, and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive comprises the following raw materials in parts by weight: 3 parts of ammonium chloride, 4 parts of nano zirconia, 2 parts of nano magnesia, 6 parts of quartz sand, 0.2 part of lanthanum nitrate, 0.12 part of cerium nitrate, 1.2 parts of sodium molybdate and 0.15 part of europium nitrate.
An inorganic additive was added to the molten S3 alloy solution of the hot-dip zinc-aluminum-nickel-tantalum alloy of this example in an amount of 0.02g/kg. And after uniformly stirring, controlling the temperature of the alloy liquid to 570 ℃, and hot-dip plating the high-silicon high-manganese steel large pipe tower piece with the discs at two ends for 3 minutes to form a plating layer with uniform thickness.
Example 4
A zinc-aluminum-nickel-tantalum alloy S4 for hot dipping comprises 10wt% of Al, 2wt% of Ni, 0.5wt% of Ta, and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive comprises the following raw materials in parts by weight: 4 parts of ammonium chloride, 3 parts of nano zirconia, 2 parts of nano magnesia, 9 parts of quartz sand, 0.4 part of lanthanum nitrate, 0.18 part of cerium nitrate, 1.8 parts of sodium molybdate and 0.18 part of europium nitrate.
An inorganic additive was added to the molten Zn-Al-Ni-Ta alloy S4 alloy solution for hot dipping of this example in an amount of 0.03g/kg. And after uniform stirring, the temperature of the alloy liquid is 590 ℃, and the tower piece of the high-silicon high-manganese steel large pipe with the welding and reinforcing steel sheets at the two ends and the middle part is hot dipped for 3 minutes.
Example 5
A zinc-aluminum-nickel-tantalum alloy S5 for hot dipping contains 5wt% of Al, 1.5wt% of Ni, 0.3wt% of Ta and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive comprises the following raw materials in parts by weight: 3.5 parts of ammonium chloride, 4 parts of nano zirconia, 1.5 parts of nano magnesia, 7 parts of quartz sand, 0.2 part of lanthanum nitrate, 0.17 part of cerium nitrate, 1.6 parts of sodium molybdate and 0.25 part of europium nitrate.
An inorganic additive was added to the molten Zn-Al-Ni-Ta alloy S5 alloy liquid for hot dipping of this example, and the amount of the inorganic additive added was 0.04g/kg. And after uniform stirring, the temperature of the alloy liquid is 590 ℃, and the square high-silicon high-manganese steel large pipe tower piece is hot dipped for 3 minutes to form a coating with uniform thickness.
Example 6
A zinc-aluminum-nickel-tantalum alloy S6 for hot dipping comprises 2wt% of Al, 0.01wt% of Ni, 0.01wt% of Ta and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive comprises the following raw materials in parts by weight: 4.5 parts of ammonium chloride, 4.5 parts of nano zirconia, 2.5 parts of nano magnesia, 7 parts of quartz sand, 0.4 part of lanthanum nitrate, 0.16 part of cerium nitrate, 1.8 parts of sodium molybdate and 0.25 part of europium nitrate.
An inorganic additive was added to the molten S6 alloy solution of the hot-dip galvanizing zinc-aluminum-nickel-tantalum alloy of this example in an amount of 0.02g/kg. And after uniformly stirring, the temperature of the alloy liquid is 570 ℃, and the common angle steel is hot-dipped for 1 minute, so that the thickness of the formed plating layer is uniform.
Example 7
A zinc-aluminum-nickel-tantalum alloy S4 for hot dipping comprises 20.0wt% of Al, 2wt% of Ni, 0.5wt% of Ta, and the balance of Zn and inevitable impurities contained in the zinc alloy.
The inorganic additive is prepared from the following raw materials in parts by weight: 2.5 parts of ammonium chloride, 4 parts of nano zirconia, 1.5 parts of nano magnesia, 6 parts of quartz sand, 0.3 part of lanthanum nitrate, 0.15 part of cerium nitrate, 1.5 parts of sodium molybdate and 0.2 part of europium nitrate.
An inorganic additive was added to the molten S7 alloy solution of the hot-dip galvanizing zinc-aluminum-nickel-tantalum alloy of the present example in an amount of 0.035g/kg. And after stirring uniformly, the temperature of the alloy liquid is 580 ℃, and the thickness of the formed coating is uniform by hot dipping the common channel steel for 2 minutes.
Test example 1
The results of the tests carried out on the samples obtained in examples 1 to 7 according to the invention and on the samples coated with the same commercially available products are shown in Table 1.
As can be seen from the above table, the sample prepared by the embodiment of the invention has the advantages of uniform plating thickness, moderate thickness, good hardness, good adhesion, bright and smooth plating layer, extremely small bottom slag amount, low iron content (0.0010-0.0085%) in half-month hot-dip galvanized alloy liquid, excellent corrosion resistance and various indexes superior to those of similar products sold in the market.
Compared with the prior art, the white rust resistant time of the invention adopting the key salt to passivate the zinc coating can reach more than 24h, and MoO on the surface layer of the metal passivation film 4 2- Can block Cl - The destruction of eroding anions enables the passive film to have cation selectivity, and the corrosion resistance of the galvanized passive film is improved; the silicate conversion film on the zinc coating resists corrosion because the inner part of the film layer is provided with negative charge SiO 3 2- Or SiO 2 Forming a protective film by the coordination of the micelle and the positively charged polymer; the rare earth metal oxide nano zirconia and nano magnesia can be used for preparing a rare earth conversion film on a metal material, and plays a role of a corrosion inhibitor in a coating, so that the corrosion resistance of the coating is improved, and a good corrosion prevention effect is achieved; the trace lanthanum nitrate and cerium nitrate have certain improvement effect on the passivation of zinc alloy, and a physical barrier formed by a compound of a passivation film cerium blocks oxygen and electrons from flowing to a cathode to inhibit a cathode reaction; the silicon dioxide modified silane solution is used for improving the mechanical property and the corrosion property of aluminum alloy and hot-dip galvanized plates; europium has excellent high-temperature oxidation resistance and corrosion resistance, and has excellent electrical properties. The inorganic additive forms a layer of passive film on the surface of the plating layer, effectively prevents the metal plating layer from being corroded, and is environment-friendly and non-toxic.
The zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention is suitable for steel materials with various complex components and complex shapes by properly selecting the types and the contents of all components in the zinc alloy, particularly adding a proper amount of Al, si, cr and Ca trace elements into a zinc bath, and can effectively control the over-rapid growth of a zinc-iron alloy layer in the hot dipping process and simultaneously reduce the alloy melting point, so that the alloy zinc bath formed after the zinc-aluminum-nickel-tantalum alloy for hot dipping provided by the invention is melted has higher fluidity, the free layer of a plating layer is thinned, the corrosion resistance and the mechanical property of the alloy plating layer can be effectively improved, the thickness of the alloy plating layer is more uniform, the color difference is avoided, the Sandlin effect is avoided, redundant zinc nodules are avoided, the plating quality is higher, iron particles in a zinc alloy liquid are reduced, the generation of bottom slag is reduced, the zinc is saved, and the zinc plating cost is reduced.
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (3)
1. A hot dip galvanizing method is characterized in that inorganic additives are added into molten zinc-aluminum-nickel-tantalum alloy liquid for hot dip galvanizing, after uniform stirring, a substrate to be galvanized is placed into the molten alloy liquid, and a coating is formed on the surface of the substrate to be galvanized;
the zinc-aluminum-nickel-tantalum alloy for hot dipping contains 2 to 25.0 weight percent of Al, 0.2 to 2 weight percent of Ni, 0.01 to 0.3 weight percent of Ta and the balance of Zn and inevitable impurities carried by the zinc alloy based on the total mass of the zinc-aluminum-nickel-tantalum alloy for hot dipping;
the inorganic additive is prepared from the following raw materials in parts by weight: 2-5 parts of ammonium chloride, 3-5 parts of nano zirconia, 1-3 parts of nano magnesia, 5-10 parts of quartz sand, 0.1-0.5 part of lanthanum nitrate, 0.1-0.2 part of cerium nitrate, 1-2 parts of sodium molybdate and 0.1-0.3 part of europium nitrate; the addition amount of the inorganic additive is 0.01-0.05g/kg.
2. The method of claim 1, wherein the substrate to be plated is one of a structural member, a steel strip, an angle steel, a plate, a flat steel, a steel pipe, and a large pipe tower member.
3. The method of claim 1, wherein the alloy liquid temperature is greater than 570 ℃.
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