CN117165888A - Zinc-based coated steel plate with excellent degreasing and phosphating performances and manufacturing method thereof - Google Patents
Zinc-based coated steel plate with excellent degreasing and phosphating performances and manufacturing method thereof Download PDFInfo
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- CN117165888A CN117165888A CN202311011549.6A CN202311011549A CN117165888A CN 117165888 A CN117165888 A CN 117165888A CN 202311011549 A CN202311011549 A CN 202311011549A CN 117165888 A CN117165888 A CN 117165888A
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- 239000011701 zinc Substances 0.000 title claims abstract description 79
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 77
- 239000010959 steel Substances 0.000 title claims abstract description 77
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 59
- 238000005238 degreasing Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000005749 Copper compound Substances 0.000 claims abstract description 14
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 6
- 239000010452 phosphate Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 16
- 238000005406 washing Methods 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- -1 zinc-aluminum-magnesium Chemical compound 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001079251 Euodia Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a zinc-based coated steel plate with excellent degreasing and phosphating performances and a manufacturing method thereof, wherein the zinc-based coated steel plate comprises a steel plate substrate, and at least one surface of the steel plate substrate comprises a zinc-based coating, a copper compound film layer and an anti-rust oil layer from the substrate to the top in sequence; the zinc-based coated steel sheet has excellent degreasing and phosphating performances, and after degreasing and phosphating, the zinc-based coated steel sheet is subjected to degreasing and phosphating at any one of 100mm 2 In the region of (2) the grain size of the phosphate film is 10 μm or less, and the difference between the maximum value and the minimum value of the grain size of the phosphate film is 5 μm or less.
Description
Technical Field
The invention belongs to the technical field of coated steel plates, and particularly relates to a zinc-based coated steel plate with excellent degreasing and phosphating performances and a manufacturing method thereof.
Background
Galvanized sheet is widely used in the field of automobile and household appliance manufacturing due to its good corrosion resistance.
In the manufacture of automobiles and household appliances, a painting step is generally required, and steel plates are generally required to be degreased to remove oil stains on surfaces before painting. In order to ensure the painting quality, the water film coverage rate after degreasing and cleaning is required to reach 100%. In recent years, low-temperature degreasing techniques have been applied in view of energy saving and environmental protection, and thus steel sheets having more excellent degreasing properties have been desired.
In practical application, it is found that hot dip Galvanized (GI) and alloyed galvanized steel sheets (GA), particularly zinc-based plated steel sheets (ZAM) and other products are more difficult to degrease than cold rolled sheets, and the problems of uneven phosphating, chromatic aberration after painting and the like are caused by discontinuous water films after degreasing frequently.
Chinese patent CN106062249a discloses a method for producing a zinc-plated steel sheet which has a small sliding resistance during press forming and is excellent in degreasing property even under severe alkali degreasing conditions of low temperature and short line length. The method for producing a zinc-plated steel sheet comprises the following steps: an oxide layer forming step of bringing a zinc-plated steel sheet into contact with an acidic solution containing sulfate ions, then holding the steel sheet for 1 to 60 seconds, and then washing the steel sheet with water; and a neutralization treatment step of holding the surface of the oxide layer formed in the oxide layer forming step in a state of being in contact with an alkaline aqueous solution containing 0.01g/L or more of P ions and 0.1g/L or more of carbonate ions for 0.5 seconds or more, followed by washing with water and drying. However, the method requires steps of acid washing, water washing, alkali washing, water washing and drying, is complex in operation, generates a large amount of wastewater, and is not beneficial to industrial production.
Chinese patent CN101437976a discloses an alloyed hot-dip galvanized steel sheet and a method for producing the same, wherein the steel sheet is hot-dip galvanized, heated to perform alloying treatment, the hot-dip galvanized steel sheet after alloying treatment is flattened, the flattened hot-dip galvanized steel sheet is allowed to stand in contact with an acidic solution containing at least one ion selected from the group consisting of Zr ion, ti ion and Sn ion for at least 1 second, and after the completion of the contact, the steel sheet is washed with water, whereby Zn-based oxides of 10nm or more are formed on the surface of the galvanized steel sheet. The steel sheet has the technical effect of improving press formability. However, this method was proposed for improving tribological properties of alloyed galvanized steel sheets (GA), and did not have the effect of improving degreasing properties.
Disclosure of Invention
The present invention provides a zinc-based plated steel sheet having excellent degreasing and phosphating properties, which is degreased and phosphatized to be 100mm at any one, and a method for producing the same 2 In the region of (2) the grain size of the phosphate film is 10 μm or less, and the difference between the maximum value and the minimum value of the grain size of the phosphate film is 5 μm or less.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a zinc-based coated steel sheet with excellent degreasing and phosphating properties comprises a steel sheet substrate, wherein at least one surface of the steel sheet substrate comprises a zinc-based coating, a copper compound film layer and an anti-rust oil layer from the substrate to the outside.
The copper compound film layer comprises 0.1-50 mg/m based on single surface 2 A copper compound.
The zinc-based coating comprises the following components in percentage by weight: 0.1 to 0.3 percent of Al, and the balance of Zn and unavoidable impurities.
The zinc-based coating comprises the following components in percentage by weight: al:0.1 to 0.3 percent, fe: 0-15%, and the balance Zn and unavoidable impurities.
The zinc-based coating comprises the following components in percentage by weight: 0.1 to 6.0 percent of Al0.1 to 3.0 percent of Mg0.1 and the balance of Zn and unavoidable impurities.
The adhesion amount of the antirust oil layer is 0.1 to 3.0g/m based on one side 2 。
The invention also provides a manufacturing method of the zinc-based coated steel plate with excellent degreasing and phosphating performances, which comprises the following steps:
(1) A zinc-based plating layer is plated on the steel plate substrate to obtain a zinc-based plated steel plate;
(2) Coating a galvanized steel sheet with an aqueous solution containing Cu ions, and drying to form a copper compound film on the surface of the zinc-based coating;
(3) And (5) coating rust-preventive oil.
In the step (1), the zinc-based coated steel sheet is obtained by cold rolling, cleaning, annealing, hot dip plating, cooling and leveling, or is obtained by hot rolling, pickling, hot dip plating, cooling and leveling.
In step (2), the coating mode includes dipping, spraying or rolling, preferably rolling.
In the step (2), the concentration of Cu ions in the aqueous solution containing Cu ions is in the range of 10 -6 ～10 -2 The mol/L, PH is acidic, and if Cu ions are likely to form precipitates in an alkaline environment.
In the step (2), the aqueous solution containing Cu ions is obtained by dissolving copper nitrate, copper sulfate, copper chloride or copper acetate in water and adjusting the pH using any one or more of sulfuric acid, citric acid and acetic acid. The sulfuric acid, the citric acid and the acetic acid are not easy to react to generate precipitation after contacting copper ions, have low volatility at room temperature, and are not easy to volatilize or decompose in the subsequent heating and drying processes so as to avoid adverse effects on equipment and environment.
In the step (2), the drying condition is heating at 60 ℃ or higher for 3s or higher, preferably heating at 60-200 ℃ for 3-60 s. Heating means include, but are not limited to, induction heating, radiant heating, hot air heating. This removes free water to form a copper compound film.
The following is to use CuSO 4 To illustrate the chemical reactions that occur during the preparation process described above. Oxidizing Cu ions and plating reaction Cu 2+ +Zn→Cu+Zn 2+ 2Cu+O under heating and gradually evaporating water 2 +4H + +2SO 4 2- →2CuSO 4 +2H 2 O. Compared with the autogenous alumina layer, cuSO 4 Has higher water affinity, promotes the degreasing fluid to infiltrate the surface of the plating layer, thereby improving the degreasing performance and improving the appearance quality and uniformity of the phosphating film. Meanwhile, in the phosphating process, Cu exists in the vicinity of the plating surface in an ionic state, and Cu occurs at this time 2+ +Zn→Cu+Zn 2+ Surface Zn of steel sheet 2+ Concentration enrichment for promoting Zn 2+ +2PO 4 3- +4H 2 O→Zn(PO 4 ) 2 ·4H 2 The O reaction is carried out to promote the rapid generation of the phosphating film, so that the effect of refining phosphating grains is achieved. In addition, the zinc-aluminum-magnesium autogenous surface aluminum oxide layer is coated with CuSO 4 Instead, the adhesive property is improved.
According to the zinc-based plated steel plate, the copper compound film layer is formed on the surface of the zinc-based plated layer of the steel plate, so that the wettability of degreasing solution on the surface of the zinc-based plated layer is increased, the problem that the zinc-based plated layer of the steel plate is difficult to degrease is solved, the appearance of a subsequently formed phosphating film is uniform, the phosphating crystallization is fine and uniform, and meanwhile, the adhesive property of the zinc-magnesium-aluminum plated layer is remarkably improved.
Compared with the prior art, the invention has the following beneficial effects:
1. in the manufacturing process of the zinc-based coated steel plate with excellent degreasing and phosphating performances, the complex steps of acid washing, water washing, alkali washing, water washing, drying and the like are not needed after the zinc-based coating is formed, a large amount of waste water is not generated, and the method has the advantages of low cost, simple and convenient working procedures and easiness in implementation.
The zinc-based coated steel plate with excellent degreasing and phosphating performances or parts manufactured by the zinc-based coated steel plate can form a uniform and complete phosphating film after degreasing, washing, surface adjustment, phosphating and optional washing steps, and the phosphating film can be formed at any one of 100mm 2 In the region of (2) the grain size of the phosphate film is 10 μm or less, and the difference between the maximum value and the minimum value of the grain size of the phosphate film is 5 μm or less.
Drawings
FIG. 1 is a photomicrograph of a phosphated film of a zinc-based coated steel sheet of example 1;
FIG. 2 is a photomicrograph of a phosphated film of the zinc-based coated steel sheet of comparative example 1;
FIG. 3 is a photograph showing the failure of the adhesive joint of the zinc-based plated steel sheet in example 1;
fig. 4 is a photograph showing failure of the adhesive joint of the zinc-based plated steel sheet in comparative example 1.
Detailed Description
The invention provides a zinc-based coated steel plate with excellent degreasing and phosphating performances, which comprises a steel plate substrate, wherein at least one surface of the steel plate substrate comprises a zinc-based coating, a copper compound film layer and an anti-rust oil layer from the substrate to the outside.
The copper content of the copper compound film layer is 0.1-50 mg/m based on single side 2 。
The zinc-based coating comprises the following components in percentage by weight: 0.1 to 0.3 percent of Al, and the balance of Zn and unavoidable impurities.
The zinc-based coating comprises the following components in percentage by weight: al:0.1 to 0.3 percent, fe: 0-15%, and the balance Zn and unavoidable impurities.
The zinc-based coating comprises the following components in percentage by weight: 0.1 to 6.0 percent of Al0.1 to 3.0 percent of Mg0.1 and the balance of Zn and unavoidable impurities.
The adhesion amount of the antirust oil layer is 0.1 to 3.0g/m based on one side 2 。
The invention also provides a manufacturing method of the zinc-based coated steel plate with excellent degreasing and phosphating performances, which comprises the following steps:
(1) A zinc-based plating layer is plated on the steel plate substrate to obtain a zinc-based plated steel plate;
(2) Coating a galvanized steel sheet with an aqueous solution containing Cu ions, and drying to form a copper compound film on the surface of the zinc-based coating;
(3) And (5) coating rust-preventive oil.
In the step (1), the zinc-based coated steel plate is obtained through cold rolling, cleaning, annealing, hot dip plating, cooling and leveling, or is obtained through hot rolling, pickling, hot dip plating, cooling and leveling; the purpose of leveling is to form irregularities on the surface of the plating layer, so that the aqueous solution containing Cu ions is more likely to contact with the plating layer and undergo chemical reaction.
In step (2), the coating mode includes dipping, spraying or rolling, preferably rolling.
In the step (2), cu ion is containedIn the aqueous solution, the concentration of Cu ions was in the range of 10 -6 ～10 -2 The mol/L and the PH are acidic, and Cu ions are easy to generate sediment under alkaline environment.
In the step (2), the aqueous solution containing Cu ions is obtained by dissolving copper nitrate, copper sulfate, copper chloride, copper acetate in water and adjusting the pH using any one or more of sulfuric acid, citric acid, and acetic acid.
In the step (2), the drying condition is heating at 60 ℃ or higher for 3s or higher, preferably heating at 60-200 ℃ for 3-60 s.
The present invention will be described in detail with reference to examples.
Examples 1 to 5 and comparative examples 1 to 3 were subjected to cold rolling, cleaning, annealing, hot dip plating, cooling, and leveling to obtain zinc-based plated steel sheets. In the following table 1, the coating composition 6.0al3.0mg represents the coating composition and weight fraction: 6.0% of Al, 3.0% of Mg and the balance of Zn and unavoidable impurities.
Example 6 and comparative example 4 hot dip galvanised clad steel sheets were obtained by cold rolling, cleaning, annealing, hot dip plating, cooling, levelling, the cladding composition and weight fraction being 0.25% Al, the balance being Zn and unavoidable impurities.
Example 7 and comparative example 5 hot dip galvannealed steel sheet (GA) was obtained by cold rolling, cleaning, annealing, hot dip coating, alloying, cooling, leveling, coating composition and weight fractions: 0.20% of Al, 10% of Fe and the balance of Zn and unavoidable impurities.
The aqueous solution containing Cu ions was pH-adjusted using sulfuric acid.
The aqueous solution containing Cu ions is uniformly coated on the surface of the steel plate coating by adopting a roller coating method.
Coating anti-rust oil quinic ferroat N6130 on the surface of the steel plate, wherein the single-sided coating amount is 1.0g/m 2 。
The plating compositions, the components of the aqueous solutions containing Cu ions used, the heating temperatures and the times of the respective examples and comparative examples are shown in Table 1.
TABLE 1
Performance evaluation was performed as follows.
The degreasing performance evaluation method comprises the following steps: the degreasing agent for the Shanghai Kaka Beijing Co., ltd., FC-L5000A (10 g/L)/FC-E2021 SB (4 g/L) is used, the degreasing agent is prepared according to the concentration of 0.5 times of the technical requirement to enhance the degreasing sensitivity, the degreasing liquid temperature is 45 ℃, the steel plate is immersed in the degreasing liquid for 2 minutes, then the steel plate is taken out and rinsed by deionized water, whether the surface of the steel plate can form a continuous water film or not is observed, the area ratio of the water film is recorded, the surface of the steel plate is covered with the water film in hundred percent, and the steel plate is OK, otherwise, the steel plate is recorded as NG.
The phosphating performance evaluation method comprises the following steps: after the degreasing was completed, phosphating was performed using a PL-X surface conditioner (Shanghai Kaka Beijing Co., ltd.) for 30 seconds (immersion), followed by ternary phosphating using Paka PB-3035 SB. The parameters of the phosphating solution are as follows: total acidity 22.0pt, free acidity 1.0pt, accelerator concentration 2.0pt, temperature 35 ℃ for 2min. And (5) washing and drying after the pretreatment is finished. Appearance evaluation of the phosphated film was performed. Cutting 10 x 10mm in any area of the sample after phosphating 2 The samples of (1) were subjected to scanning electron microscopy for observing grain size and uniformity (difference between maximum grain size and minimum grain size).
The adhesive performance test method comprises the following steps: compatibility with the sealing damping compound (Evodia RA240 adhesive) was evaluated, and a single lap joint test was performed according to SAE J1523 standard, and the specimen failure mode ratio was recorded. The result evaluation method comprises the following steps: the ideal failure mode is the peeling between the glue, known as cohesive failure; the undesirable result is peeling between the glue and the steel sheet, indicating poor compatibility of the steel with the glue, known as interfacial failure.
The evaluation results are shown in Table 2.
Table 2 results of performance evaluation
The examples significantly improved degreasing properties of the zinc-based plated steel sheet as compared to comparative example 1/2/3/4/5. Example 1 significantly improved degreasing performance compared to comparative example 1, which did not use a copper ion solution, demonstrating that the copper ion-containing surface treatment had better degreasing performance. In comparative example 2, when the Cu ion content is less than 10 -6 A decrease in degreasing properties was observed in mol/L.
Compared with the comparative example, the embodiment obviously improves the appearance quality of the phosphating film of the zinc-series coated steel plate, refines the crystal size of the phosphating film and ensures that the distribution of phosphating grains is more uniform. Fig. 1 and 2 show micrographs of the phosphor films of example 1 and comparative example 1, respectively, showing that the phosphor film of example 1 has uniform grains and the phosphor film of comparative example 1 has non-uniform size. Example 1 significantly improved phosphating performance compared to comparative example 1, which did not use a solution of copper ions, demonstrating that surface treatment with copper ions had better phosphating performance.
Compared with comparative examples 1/2/3, examples 1 to 5 significantly improved the cohesive failure mode ratio of the adhesive joints of zinc-magnesium-aluminum coated steel sheets, and improved the adhesive properties. Fig. 3 is a photograph showing the failure of the adhesive joint of example 1 and comparative example 1, and it can be seen that example 1 is cohesive failure, tearing between the adhesives, and demonstrating that the compatibility of the steel sheet and the adhesives is good, whereas comparative example 1 is tearing between the adhesives, breaking at the interface failure, and the compatibility of the steel sheet and the adhesives is poor. Example 1 significantly improved the adhesive properties compared to comparative example 1, which does not use a solution of copper ions. In comparison with comparative examples 4/5, examples 6/7 did not improve but did not reduce the adhesive properties due to the better adhesive properties of the GI, GA products themselves.
The foregoing detailed description of a zinc-based coated steel sheet having excellent degreasing and phosphating properties and a method for manufacturing the same, which are illustrative and not restrictive, are exemplified by several examples within the scope of the present invention without departing from the general inventive concept, and therefore, should be construed as falling within the scope of the present invention.
Claims (10)
1. The zinc-based coated steel plate with excellent degreasing and phosphating performances is characterized by comprising a steel plate substrate, wherein at least one surface of the steel plate substrate comprises a zinc-based coating, a copper compound film layer and an anti-rust oil layer from the substrate to the outside.
2. The zinc-based plated steel sheet having excellent degreasing and phosphating properties as claimed in claim 1, wherein the copper compound film layer comprises 0.1 to 50mg/m in terms of one side 2 A copper compound.
3. The zinc-based plated steel sheet having excellent degreasing and phosphating properties according to claim 1, wherein the zinc-based plating comprises the following components in weight percentage: 0.1 to 0.3 percent of Al, and the balance of Zn and unavoidable impurities.
4. The zinc-based plated steel sheet having excellent degreasing and phosphating properties according to claim 1, wherein the zinc-based plating comprises the following components in weight percentage: al:0.1 to 0.3 percent, fe: 0-15%, and the balance Zn and unavoidable impurities.
5. The zinc-based plated steel sheet having excellent degreasing and phosphating properties according to claim 1, wherein the zinc-based plating comprises the following components in weight percentage: 0.1 to 6.0 percent of Al0.1 to 3.0 percent of Mg0.1 and the balance of Zn and unavoidable impurities.
6. The zinc-based plated steel sheet having excellent degreasing and phosphating properties as claimed in claim 1, wherein the amount of the rust inhibitive oil layer attached is 0.1 to 3.0g/m in terms of one side 2 。
7. The method for producing a zinc-based plated steel sheet having excellent degreasing and phosphating properties as defined in any one of claims 1 to 6, comprising the steps of:
(1) A zinc-based plating layer is plated on the steel plate substrate to obtain a zinc-based plated steel plate;
(2) Coating a galvanized steel sheet with an aqueous solution containing Cu ions, and drying to form a copper compound film on the surface of the zinc-based coating;
(3) And (5) coating rust-preventive oil.
8. The method according to claim 7, wherein in the step (2), the concentration of Cu ions in the aqueous solution containing Cu ions is in the range of 10 -6 ～10 -2 mol/L, and the PH is neutral or acidic.
9. The method according to claim 8, wherein in the step (2), the aqueous solution containing Cu ions is obtained by dissolving copper nitrate, copper sulfate, copper chloride or copper acetate in water and adjusting the pH with any one or more of sulfuric acid, citric acid and acetic acid.
10. The method according to claim 7, wherein in the step (2), the drying condition is 60 ℃ or higher and heating is performed for 3 seconds or longer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311011549.6A CN117165888A (en) | 2023-08-11 | 2023-08-11 | Zinc-based coated steel plate with excellent degreasing and phosphating performances and manufacturing method thereof |
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| CN202311011549.6A CN117165888A (en) | 2023-08-11 | 2023-08-11 | Zinc-based coated steel plate with excellent degreasing and phosphating performances and manufacturing method thereof |
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| CN117165888A true CN117165888A (en) | 2023-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311011549.6A Pending CN117165888A (en) | 2023-08-11 | 2023-08-11 | Zinc-based coated steel plate with excellent degreasing and phosphating performances and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117165888A (en) |
-
2023
- 2023-08-11 CN CN202311011549.6A patent/CN117165888A/en active Pending
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