KR20120056588A - Galvanized steel sheet having excellent coatability and coating adhesion - Google Patents

Galvanized steel sheet having excellent coatability and coating adhesion Download PDF

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KR20120056588A
KR20120056588A KR1020100118201A KR20100118201A KR20120056588A KR 20120056588 A KR20120056588 A KR 20120056588A KR 1020100118201 A KR1020100118201 A KR 1020100118201A KR 20100118201 A KR20100118201 A KR 20100118201A KR 20120056588 A KR20120056588 A KR 20120056588A
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South Korea
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plating
steel sheet
galvanized steel
content
sol
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KR1020100118201A
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Korean (ko)
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김명수
김영하
이주연
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주식회사 포스코
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Priority to KR1020100118201A priority Critical patent/KR20120056588A/en
Publication of KR20120056588A publication Critical patent/KR20120056588A/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon

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  • 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

One aspect of the present invention is a weight percent, C: 0.07 ~ 0.15%, Mn: 1.0 ~ 2.5%, Si: 0.7 ~ 2.0%, Sol. Al: 0.03 ~ 0.15%, the balance Fe and other unavoidable impurities And by providing a hot dip galvanized steel sheet excellent in plating adhesion,
It is possible to secure excellent balance of strength and ductility by providing TRIP steel as target steel type, and improve plating property and plating adhesion during hot dip galvanizing by controlling the shape of oxide formed on the surface of steel sheet by controlling Al content. It may be advantageous to obtain a hot dip galvanized steel sheet having excellent plating quality.

Description

Hot-dip galvanized steel sheet excellent in plating property and adhesiveness {GALVANIZED STEEL SHEET HAVING EXCELLENT COATABILITY AND COATING ADHESION}

The present invention relates to a hot-dip galvanized steel sheet excellent in plating properties and plating adhesion, and improves the plating property and plating adhesion during hot dip galvanizing by spheroidizing the forms of oxides such as Mn and Si formed on the surface through Al content control. It relates to a hot dip galvanized steel sheet.

As the competition in the existing automobile industry intensifies, there is a demand for higher quality and diversification of automobile quality.In particular, in order to satisfy more stringent safety and environmental regulations, the strength of steel sheet itself is increased, and thus the weight of automobile steel sheet is increased. I'm trying to.

However, since the increase in strength generally leads to a decrease in ductility, there is no limit to increasing the strength of the steel sheet. To solve this problem, Transformation Induced Plasticity (TRIP) having excellent balance between strength and ductility is solved. The development of the residual austenite steel has continued.

TRIP steel is intended to improve the ductility by distributing residual austenite in polygonal ferrite or bainite structure, causing residual austenite to undergo metamorphic organic plasticity at the beginning of processing. In general, TRIP steel is sufficiently secured by retaining austenite through addition of Si, and cooling is performed under appropriate conditions so that pearlite transformation does not occur when the austenite is cooled. In this way, part of the austenite is transformed to martensite in the final cooling, and the rest is left.

That is, conventionally, by adding a large amount of alloying elements such as Si and controlling the cooling conditions to form a large amount of retained austenite that generates metamorphic organic plasticity, it was possible to ensure excellent strength and ductility simultaneously.

However, components such as Mn and Si added to the TRIP steel are concentrated on the surface of the steel sheet during annealing to form oxides such as MnO and SiO 2 . It is generally used in automobiles, building structures, and home appliances by performing hot dip galvanizing on TRIP steel to secure corrosion resistance. Unplated phenomenon occurs or plating is caused by oxides such as MnO and SiO 2 formed on the surface of the steel sheet. Even if this is achieved, there is a problem that the zinc plated layer is dropped during processing due to poor adhesion, and in the past, there was no limit to applying TRIP steel to hot-dip galvanized steel sheet.

Therefore, it is time to develop a TRIP steel with excellent plating quality by solving the above problems and improving the plating property and plating adhesion when the hot dip galvanization of TRIP steel is applied.

The present invention controls the form of the surface oxide in forming the surface oxide by concentrating the components of Mn, Si and the like on the surface of the steel sheet in the annealing process, thereby improving the plating quality and improved plating adhesion during hot dip galvanizing Provide galvanized steel sheet.

One aspect of the present invention is a weight percent, C: 0.07 ~ 0.15%, Mn: 1.0 ~ 2.5%, Si: 0.7 ~ 2.0%, Sol. Al: 0.03 ~ 0.15%, the balance Fe and other unavoidable impurities And it provides a hot-dip galvanized steel sheet excellent in plating adhesion.

In this case, the steel sheet preferably further comprises Ti: 0.03% or less (excluding 0%), P: 0.03% or less (excluding 0%), and Sb: 0.05% or less (excluding 0%).

According to one aspect of the present invention, by providing a TRIP steel as the target steel, it is possible to ensure a good balance of strength and ductility, and to control the shape of the oxide formed on the surface of the steel sheet by controlling the Al content during hot dip galvanizing It is possible to improve the plating property and plating adhesion, and thus it may be advantageous to obtain a hot-dip galvanized steel sheet having excellent plating quality.

Figure 1 shows the surface state of the cold rolled steel sheet according to the Al content in a SEM picture.
Figure 2 shows the surface state of the hot-dip galvanized steel sheet according to the Al content.
3 is a graph showing the evaluation score of the plating according to the Al content.

In the case of a conventional high strength cold rolled steel sheet (TRIP), components such as Mn, Si, and Al contained in the base steel sheet are concentrated on the surface during annealing to form a reticulated surface oxide. There was a problem that the plating layer dropout phenomenon occurs during the plating phenomenon and processing.

Therefore, the present inventors have recognized that by controlling the content of Sol.Al after a long study, the shape of the surface oxide of high strength cold rolled steel sheet can be changed into a spherical shape, thereby improving the plating property and plating adhesion during hot dip galvanizing. It was.

That is, the present invention basically uses the component system and composition range of the TRIP steel, which can ensure excellent strength and ductility, and in particular, the shape of the surface oxide can be changed by specially controlling the Al content, and thus the plating quality. Provided is a hot-dip galvanized steel sheet excellent in plating property and plating adhesion which can be improved.

Hereinafter, the steel plate of this invention is demonstrated.

One aspect of the present invention is a weight percent, C: 0.07 ~ 0.15%, Mn: 1.0 ~ 2.5%, Si: 0.7 ~ 2.0%, Sol. Al: 0.03 ~ 0.15%, the balance Fe and other unavoidable impurities And it provides a hot-dip galvanized steel sheet excellent in plating adhesion.

Hereinafter, the component system (weight%) of the said steel plate is demonstrated.

Carbon (C): 0.07-0.15%

C is added to secure the strength of the steel sheet as an austenite stabilizing element, and the amount of C added is preferably controlled to 0.07 to 0.15%. If the addition amount is less than 0.07%, the amount is too small, there is no limit to securing the strength of the steel sheet, there is a problem that it is difficult to secure the residual austenite, if the addition amount exceeds 0.15% is inferior to weldability Since a problem arises, it is necessary to control the addition amount to 0.07 to 0.15% as mentioned above.

Manganese (Mn): 1.0-2.5%

Mn is an austenite stabilizing component, and the amount of Mn added is preferably controlled at 1.0 to 2.5%. If the addition amount is less than 1.0%, the amount is too small to limit strength, and the residual amount of austenite is also significantly reduced. If the addition amount is more than 2.5%, weldability is deteriorated and an oxide is formed on the surface during annealing. Since the amount of is so large that it is not easy to secure the plating property and plating adhesion during hot dip galvanization even within the appropriate Al content range, it is preferable to control the addition amount to 1.0 to 2.5% as described above.

Silicon (Si): 0.7 ~ 2.0%

Si is a component that suppresses the precipitation of cementite and contributes to the formation and stabilization of residual austenite, and the amount of Si added is preferably controlled to 0.7 to 2.0%. If the addition amount is less than 0.7%, it is difficult to suppress the formation of cementite during annealing, so that materials such as ductility deteriorate. If the addition amount is more than 2.0%, the amount of oxide formed on the surface during annealing is too large. Even within an appropriate Al content range, it is not easy to secure plating property and plating adhesion during hot dip galvanizing, and therefore, it is preferable to control the addition amount to 0.7 to 2.0% as described above.

Acid-soluble aluminum (Sol.Al): 0.03 ~ 0.15%

Sol.Al is an essential component for securing the plating quality through the surface oxide shape control of the present invention, and the addition amount thereof is preferably controlled at 0.03 to 0.15%. If the addition amount is less than 0.03%, the oxide formed on the surface of the steel sheet in the annealing process exhibits a reticular shape, and even though hot dip galvanized thereon, unplating or plating peeling occurs easily, and it is difficult to secure materials. When the addition amount is more than 0.15%, the amount is too large to form a large amount of Al 2 O 3 oxide on the surface of the steel sheet, especially the surface oxide has a large reticulated shape, the plating property and plating adhesion during hot dip galvanizing It is difficult to secure well.

Therefore, it is important to control the addition amount to 0.03 to 0.15%, and as a result of a long study by the present inventors, when Sol.Al has the content, it is possible to make the surface oxide appear as a fine spherical shape, and the surface of such shape When hot-dip galvanizing on the oxide was found to be excellent in plating properties and to prevent the plating peeling during processing. Particularly, when the addition amount of Sol.Al is more preferably 0.05 to 0.1%, it is found that the hot dip galvanized steel sheet having excellent plating quality is excellent because the plating property and plating peeling phenomenon are more excellent.

In addition, the steel sheet preferably further comprises Ti: 0.03% or less (excluding 0%), P: 0.03% or less (excluding 0%), and Sb: 0.05% or less (excluding 0%).

Titanium (Ti) is a component that can be additionally added to secure the strength, and if the addition amount exceeds 0.03%, the ductility may be inferior. Therefore, the content is less than 0.03% (excluding 0%). It is desirable to control.

Phosphorus (P) is also a component that can be additionally added to ensure strength, and if the addition amount exceeds 0.03%, the steel material characteristics may be inferior due to P segregation. 0% is excluded).

Antimony (Sb) is a component that can be additionally added to prevent decarburization of the surface layer, and if the addition amount exceeds 0.05%, the steel material properties may be poor due to grain boundary segregation. It is preferable to control to% or less (except 0%).

Other components may be added as appropriate to secure the material properties of the steel, as it has been added to the conventional TRIP steel, and the process and conditions of the manufacture of the TRIP steel and hot dip galvanizing are appropriate for those skilled in the art. By selecting and controlling in such a way, it is possible to manufacture a hot-dip galvanized steel sheet excellent in plating property and plating adhesion with the above composition.

Hereinafter, the present invention will be described in detail by way of examples, which are intended for a more complete description of the present invention, and the scope of the present invention is not limited by the following individual examples.

( Example )

In the present invention, after dissolving the components shown in Table 1 and then hot-rolled and cold-rolled in a conventional manner, the steel sheet supplied through a degreasing process to clean the surface of the steel sheet and blow nitrogen gas containing 5% hydrogen in a reducing atmosphere. After annealing for 820 ° C for 60 seconds, the steel sheet cooled according to the conventional TRIP steel heat treatment cycle was immersed for 3 seconds at an effective Al concentration of 0.2% and a galvanizing bath temperature of 460 ° C, and then air wipping. The plating adhesion amount coated on the surface was to maintain the level of 60g / ㎡.

Category (% by weight) C Mn Si Sol.Al Ti P Sb Inventory 1 0.07 1.5 0.9 0.05 - 0.02 - Inventory 2 0.08 1.6 1.5 0.03 - 0.02 - Inventory 3 0.15 1.6 1.5 0.1 - 0.02 - Honorable 4 0.1 2 1.2 0.1 0.01 - 0.01 Inventory 5 0.15 1.5 1.2 0.07 0.02 0.01 - Inventory 6 0.1 3 1.8 0.13 - - 0.02 Honorable 7 0.15 1.7 1.5 0.08 0.01 0.025 0.03 Comparative Example 1 0.1 1.5 1.5 0.01 - - - Comparative Example 2 0.15 1.4 1.7 0.2 - 0.02 - Comparative Example 3 0.1 2 1.2 0.5 - 0.02 - Comparative Example 4 0.1 1.5 One 0.3 0.01 0.02 0.02 Comparative Example 5 0.08 5 1.2 0.05 - 0.02 - Comparative Example 6 0.1 One 2.5 0.07 - 0.15 0.02 Comparative Example 7 0.15 4 3 0.25 0.1 - -

In order to evaluate the plating property of the hot-dip galvanized steel sheet after the plating process, the coating area ratio of the Zn layer to the total surface area of the plated surface was measured, and the results are shown in Table 2. In addition, in order to measure the plating adhesion of the hot-dip galvanized steel sheet, a bending test was performed after bending a specimen having a size of 30 x 80 mm2 at a 180 ° angle. Depending on the material properties of the steel sheet, 0T or 1T bending was performed in a range where the material did not break. When the transparent vinyl tape was attached to the bending part and then peeled off, the plating layer appeared as 'peeled'.

division Zinc plating coverage (%) Plating rating Peel off Plating adhesion evaluation Inventory 1 100 Very good Unpeeled Great Inventory 2 96 Great Unpeeled Great Inventory 3 99 Very good Unpeeled Great Honorable 4 100 Very good Unpeeled Great Inventory 5 99 Very good Unpeeled Great Inventory 6 97 Great Unpeeled Great Honorable 7 99 Very good Unpeeled Great Comparative Example 1 55 Inferior Peeling Inferior Comparative Example 2 40 Very inferior Peeling Inferior Comparative Example 3 10 Very inferior - - Comparative Example 4 35 Very inferior Peeling Inferior Comparative Example 5 60 Inferior Peeling Inferior Comparative Example 6 35 Very inferior Peeling Inferior Comparative Example 7 <5 Very inferior - -

Experimental results, Inventive Examples 1 to 7 all the essential components such as Mn, Si was found to satisfy the scope of the present invention both excellent plating and plating adhesion. In particular, all of the Sol.Al satisfy the range 0.03 ~ 0.15% by weight of the present invention, the surface oxide formed during the annealing showed a fine spherical shape, so that the unplated or peeling phenomenon hardly occurs during hot dip galvanizing It can be seen that.

In particular, inventive examples 1, 3, 4, 5, and 7 have a zinc plating coverage of up to 99 to 100% because the Sol.Al range satisfies 0.05 to 0.1% by weight, which is a more preferable range. I could confirm that.

On the contrary, in Comparative Example 1, since the content of Sol.Al was 0.01% by weight, which is much lower than the range of the present invention, the plating property was inferior, and it was confirmed that the plating peeling phenomenon also appeared. It can be interpreted that the surface oxides have a reticular shape because the content of Sol.Al is too small, so that the plating property and the plating adhesion property are not good at the time of hot dip galvanizing.

In Comparative Examples 2 and 4, since the content of Sol.Al was higher than the range of the present invention, the surface oxide showed a large reticular shape, and it was found that a large amount of Al oxide was formed, resulting in inferior plating and adhesion. .

In Comparative Example 3, since the content of Sol.Al was 0.5% by weight, which was much larger than the range of the present invention, the zinc coating coverage was very bad at 10%, and thus, the plating peeling experiment itself could not be performed.

In Comparative Examples 5 and 6, the content of Sol.Al satisfies the scope of the present invention, but it was confirmed that the content of Mn and Si was not good in the plating property and the plating adhesiveness, respectively. That is, only the Sol.Al range is satisfied, and the plating and adhesion are not always excellent, but all the essential components of the present invention, such as Sol.Al, Mn, and Si, must satisfy the composition range of the present invention to ensure excellent plating quality. Able to know.

In Comparative Example 7, Mn, Si, and Sol. Al all exceeded the range of the present invention, and the zinc plating coverage was extremely poor at less than 5%, and thus, plating peeling experiments could not be performed.

The present inventors conducted further experiments as follows in order to grasp the change of the surface oxide state according to the Al content in more detail. First, in weight percent, C: 0.09%, Mn: 1.6%, Si: 1.5%, and the Sol.Al content is 0.01, 0.1, 0.3, 0.5%, respectively, a total of four steels consisting of the balance Fe and other unavoidable impurities. The slab was manufactured in the same condition as the above experiment, and the cold rolled steel sheet was manufactured. The surface photographs of three cold rolled steel sheets having an Al content of 0.01, 0.1, and 0.3% were shown in FIG. 1.

Then, after performing hot dip galvanizing on four cold rolled steel sheets having Al content of 0.01, 0.1, 0.3, and 0.5% under the same conditions as in the above experiment, the surface photographs showing the plating state of the galvanized steel sheet are shown in FIG. And, after performing the plating test evaluation by changing the Al content, respectively, this is shown in the graph in FIG. The evaluation of the plating property shown in Figure 3 scored from 1 point to 5 points in excellent order in the order in which the plating properties are inferior.

First, when the analysis of Figures 1 and 2, when the Al content is 0.01% (a), the oxide formed on the surface of the cold-rolled steel sheet exhibited a reticular shape, a considerable amount of unplated portion is formed on the surface of the hot-dip galvanized steel sheet, the surface oxide It can be seen that the plating quality is deteriorated due to the shape of.

Next, when the Al content is 0.1% (b), the oxide on the surface of the cold-rolled steel sheet appeared to be a fine spherical shape, it can be confirmed that the unplated portion is hardly appeared on the surface of the hot-dip galvanized steel sheet, the plating property was very excellent. . In other words, when hot dip galvanizing was performed on the fine spherical surface oxide, it was found that the plating property was excellent and the plating quality could be improved.

In addition, when the Al content is 0.3% (c), the surface oxide of the cold-rolled steel sheet appeared to be a large reticular form, and thus a large amount of unplated portions were formed on the surface of the hot-dip galvanized steel sheet, resulting in poor plating quality due to the shape. You can see that it is done. Particularly, when the Al content was 0.5% (d), since Al oxide was formed on the surface in addition to the shape, a large amount of Al oxide was formed on the surface of the hot-dip galvanized steel sheet, indicating that the plating property was extremely poor. .

In the case of a in the case of a was added to the Si as 1.5% by weight as described above, in the case of b was lowered Si slightly added to 1.3% by weight was tested, the content of the Sol.Al plated in the range of 0.03 ~ 1.5% by weight This was excellent, and it can be confirmed that especially the best plating property was shown in the range of 0.05 to 0.1 weight%.

Claims (2)

By weight%, C: 0.07 ~ 0.15%, Mn: 1.0 ~ 2.5%, Si: 0.7 ~ 2.0%, Sol.Al: 0.03 ~ 0.15%, Residual Fe and other unavoidable impurities. galvanized steel.
The method according to claim 1,
Hot-dip galvanized steel sheet with excellent plating and adhesion properties further comprising Ti: 0.03% or less (excluding 0%), P: 0.03% or less (excluding 0%), and Sb: 0.05% or less (excluding 0%) .
KR1020100118201A 2010-11-25 2010-11-25 Galvanized steel sheet having excellent coatability and coating adhesion KR20120056588A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108474094A (en) * 2015-12-22 2018-08-31 杰富意钢铁株式会社 Alloy galvanized steel plate containing Mn and its manufacturing method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108474094A (en) * 2015-12-22 2018-08-31 杰富意钢铁株式会社 Alloy galvanized steel plate containing Mn and its manufacturing method
CN108474094B (en) * 2015-12-22 2020-06-19 杰富意钢铁株式会社 Mn-containing alloyed hot-dip galvanized steel sheet and method for producing same
US11136641B2 (en) 2015-12-22 2021-10-05 Jfe Steel Corporation Mn-containing galvannealed steel sheet and method for producing the same

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