WO2022139367A1 - 실러 접착성이 우수한 도금 강판 및 이의 제조방법 - Google Patents
실러 접착성이 우수한 도금 강판 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2022139367A1 WO2022139367A1 PCT/KR2021/019405 KR2021019405W WO2022139367A1 WO 2022139367 A1 WO2022139367 A1 WO 2022139367A1 KR 2021019405 W KR2021019405 W KR 2021019405W WO 2022139367 A1 WO2022139367 A1 WO 2022139367A1
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- WIPO (PCT)
- Prior art keywords
- plating layer
- steel sheet
- phase
- plating
- plated steel
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 76
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- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- 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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
Definitions
- the present invention relates to a plated steel sheet having excellent sealer adhesion and a method for manufacturing the same.
- the zinc plating method which suppresses corrosion of iron through cathodic corrosion, has excellent corrosion resistance performance and economical efficiency, and is widely used to manufacture steel materials with high corrosion resistance.
- hot-dip galvanized steel which forms a plating layer by immersing steel in molten zinc, has a simpler manufacturing process and lower product price than electro-galvanized steel. Its demand is increasing.
- the Zn-Al-Mg-based plated steel sheet may have inferior adhesion to the adhesive due to the formation of MgO-based oxide on the surface layer compared to the general galvanized steel sheet.
- the adhesion of automobile steels is in progress by using both spot welding and adhesive attachment. For this reason, the importance of securing the adhesion between the adhesive and the steel plate is gradually being emphasized. If the adhesion between the adhesive and the steel plate is not secured, the adhesive failure occurs. If the adhesion between the steel plate and the adhesive is sufficient, cohesive failure occurs within the adhesive.
- There are two major methods to improve the adhesiveness of the product It is necessary to develop an adhesive suitable for a highly corrosion-resistant plated steel sheet or to change the structure of the surface of a highly corrosion-resistant plated layer.
- the first method has the disadvantage that the processing cost increases because R&D cost and additional process are required because a new adhesive must be applied to the existing bonding process for automobiles, and it may take a long time for development. Accordingly, there is a need to develop a technology that secures adhesion while using the adhesive used in the existing hot-dip galvanizing.
- the above method has disadvantages in that the production cost increases because an additional post-treatment process is required, and thereafter, it is inconvenient to remove the post-treatment material at an additional process cost in the automobile manufacturing process.
- As another method there is a case where the surface layer is lightly acid washed with hydrochloric acid after plating. It is a method of disposing of the MgO oxide of the surface layer and forming a metal plating layer on the surface layer, but this method also has a disadvantage in that additional facilities and costs are generated.
- the first method is to apply a skin pass mill with a hard chrome coating to destroy the MgO-based oxide formed on the surface layer so that the adhesive can react with the metallic plating layer of the MgO oxide lower layer. to be.
- the above-described method carries a risk of causing other surface defects such as dents due to excessive skin pass mill pressing.
- Another method is to remove the surface layer MgO oxide after plating through mechanical brushing of the surface layer oxide.
- the above method may cause scratches on the surface, it is difficult to remove the residue formed after polishing, and it has a disadvantage that requires an investment in equipment because an abrasive brush and a rinse equipment are additionally required.
- Patent Document 1 Korean Publication No. 2013-0133358
- One aspect of the present invention is
- Fe-Al-based suppression layer provided between the base iron and the Zn-Mg-Al-based plating layer;
- the plating layer contains, by weight, Mg: 1.0 to 2.0%, Al: 1.0 to 3.0%, the balance Zn and other unavoidable impurities,
- the ratio of Zn single phase on the surface of the plating layer is 50% or more in area fraction
- the average diameter of the Zn single phase on the surface of the plating layer is 3 ⁇ 20 ⁇ m, to provide a plated steel sheet.
- Hot-dip galvanizing by immersing the secondary cooled base iron in weight %, Mg: 1.0 to 2.0%, Al: 1.0 to 3.0%, and a plating bath containing the remainder Zn and other unavoidable impurities; and
- It provides a method for manufacturing a plated steel sheet, including.
- Example 1 is a comparison of the temperature increase and cooling temperature curves of Inventive Example 1 and Comparative Example 1 steel sheet.
- the inventors of the present invention as a result of intensive studies to improve the adhesion between the plating layer and the adhesive such as the sealer at the same time as excellent corrosion resistance, found that the microstructure on the surface of the plating layer is a very important element, and came to complete the present invention. It will be described in detail below.
- a plated steel sheet according to an aspect of the present invention Soji-cheol; and a Zn-Mg-Al-based plating layer provided on at least one surface of the base iron.
- the type of the base iron is not particularly limited, for example, as the base iron, a Fe-based base iron used as a base iron of a conventional zinc-based or zinc alloy-based steel sheet (that is, a hot-rolled steel sheet or cold rolled steel sheet), etc. can be used.
- the base iron carbon steel, ultra-low carbon steel, or high manganese steel used as a material for construction, home appliances, automobiles, and wire rods may be applied without limitation.
- C greater than 0% and less than or equal to 0.17%
- Si greater than 0% and less than or equal to 1.5%
- Mn 0.01 to 2.7%
- P greater than 0% and less than or equal to 0.07%
- S greater than 0% and less than or equal to 0.015 % or less
- Al greater than 0% and less than or equal to 0.5%
- Nb greater than 0% and less than or equal to 0.06%
- Cr greater than or equal to 1.1% (including 0%)
- Ti greater than 0% and less than or equal to 0.06%
- B greater than 0% and less than or equal to 0.03%
- base iron having a composition containing the remainder Fe and other unavoidable impurities.
- the Zn-Mg-Al-based plating layer may be formed on only one surface of the base iron, or may be formed on both surfaces of the base iron.
- the Zn-Mg-Al-based plating layer refers to a plating layer that contains Mg and Al made of a Zn-Mg-Al-based alloy, but an excess of Zn.
- the Zn-Mg-Al-based plating layer includes, by weight, Mg: 1.0 to 2.0%, Al: 1.0 to 3.0%, the balance Zn and other unavoidable impurities.
- Mg 1.0 to 2.0%
- Al 1.0 to 3.0%
- the balance Zn and other unavoidable impurities the reason for adding each component in the Zn-Mg-Al-based plating layer and the reason for limiting the content will be described.
- the Mg in the zinc alloy plating layer is an element that improves the corrosion resistance of the plated steel material. If the content is too low, there is a problem in that the effect of improving corrosion resistance is insignificant. Therefore, the lower limit of the Mg content in the zinc alloy plating layer is preferably 1.0% by weight, more preferably 1.2% by weight. However, if the content is excessive, the formation of a coarse MgZn 2 phase on the surface layer due to Mg oxidation in the plating bath is induced a lot, and a large distribution of the Zn/MgZn 2 binary phase may be formed. can be formed Therefore, the upper limit of the Mg content in the zinc alloy plating layer is preferably 2.0% by weight.
- Al in the zinc alloy plating layer is an element that suppresses Mg oxide. If the content is too low compared to the Mg content, the Mg oxidation prevention effect in the plating bath is insignificant. Therefore, the lower limit of the Al content in the zinc alloy plating layer is preferably 1.0 wt%. However, when the content is excessive, there is a problem in that the plating bath melting temperature must be increased. If the plating bath temperature is high, corrosion of the plating bath or internal equipment and excessive ash generation are caused.
- the upper limit of the Al content in the zinc alloy plating layer is 3.0% by weight, which may induce the formation of a fine Zn/MgZn 2 /Al ternary eutectic structure in the surface layer of the plating layer.
- the lower limit of the Al content may be 1.5%, or the upper limit of the Al content may be 2.5%.
- the content ratio of Mg/Al should be adjusted to 0.6 or more and 0.9 or less to obtain a beautiful plating product with a high distribution of the ternary phase. Meanwhile, in terms of further improving the surface quality, the lower limit of the Mg/Al content ratio may be 0.67, or the upper limit of the Mg/Al content ratio may be 0.88.
- the remainder may be Zn and other unavoidable impurities.
- Inevitable impurities may be included as long as they can be unintentionally mixed in the manufacturing process of a conventional hot-dip zinc-based or zinc-alloy-coated steel sheet, and those skilled in the art can easily understand the meaning, so that the present invention specifically limits them.
- the Zn-Mg-Al-based plating layer may contain a small amount of iron (Fe) component diffused from the base iron, but in the present invention, the content corresponds to a very small impurity level, so it is not separately defined.
- a Fe-Al-based suppression layer (so-called, an inhibition layer) is formed between the base iron and the Zn-Mg-Al-based plating layer.
- the Fe-Al-based suppression layer is a layer containing an intermetallic compound of Fe and Al (or a layer consisting of an intermetallic compound of Fe and Al), and the intermetallic compound of Fe and Al is, for example, FeAl , FeAl 3 , Fe 2 Al 5 and the like.
- the Fe-Al-based suppression layer may include, by weight, Fe: 30-50%, Al: 50-70%, and the Fe-Al-based suppression layer is commonly applied in the art. The description is equally applicable. That is, the Fe-Al-based suppression layer may further include (eg, 40% or less) of components derived from the plating layer such as Zn, Mg, Si, etc. in addition to Fe and Al.
- This Fe-Al-based suppression layer is a layer formed by alloying by the components of the plating bath and Fe diffused from the base iron in the initial plating.
- the Fe-Al-based suppression layer not only serves to improve the adhesion between the base iron and the Zn-Mg-Al-based plating layer, but also prevents the diffusion of Fe from the base iron to the Zn-Mg-Al-based plating layer. It also serves as an inhibitory layer.
- the thickness of the Fe-Al-based suppression layer may be 20 ⁇ 100nm.
- the lower limit of the thickness of the Fe-Al-based suppression layer may be 20 nm in order to prevent alloying and secure corrosion resistance.
- the upper limit of the thickness of the Fe-Al-based suppression layer may be 100 nm.
- the thickness of the Fe-Al-based suppression layer may mean the minimum thickness in the thickness direction (direction perpendicular to the rolling direction) from the interface with the base steel sheet.
- the microstructure of the Zn-Mg-Al-based plating layer is not particularly limited, but Zn single phase, Zn-MgZn 2 phase (ie, Zn/MgZn 2 binary process structure) and Zn-MgZn 2 -Al phase (ie, Zn/MgZn 2 /Al ternary eutectic structure).
- Zn single phase, Zn-MgZn 2 phase, Zn/MgZn 2 binary process structure) and Zn-MgZn 2 -Al phase ie, Zn/MgZn 2 /Al ternary eutectic structure.
- MgZn 2 phase, Al-Zn phase, etc. may be further included as other phases.
- a method of confirming the microstructure of the Zn-Mg-Al-based plating layer there is a method of using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) by enlarging the cross-sectional magnification of the plating layer.
- SEM scanning electron microscope
- TEM transmission electron microscope
- the Zn single phase refers to a phase mainly composed of Zn, specifically, a phase containing 95 wt% or more of Zn. That is, the Zn single phase means a phase in which Al, Mg, etc., which can be included as components of the plating layer other than Zn, may be dissolved in 5% or less (including 0%) or may be precipitated in the Zn single phase, with the balance being Zn.
- the Zn-MgZn 2 -Al phase means a ternary eutectic phase including all of the Zn phase, the MgZn 2 phase, and the Al phase.
- the MgZn 2 phase means a phase mainly composed of MgZn 2
- the Zn-MgZn 2 phase means a binary eutectic phase of a lamellar structure including a Zn phase and a MgZn 2 phase
- the Al-Zn phase is an Al phase It means a binary eutectic phase of a lamellar structure including a Zn phase or a mixed structure of an Al phase and a Zn phase with a fine diameter.
- the ratio of the Zn single phase on the surface of the plating layer may be 50% or more (excluding 100%) as an area fraction, and more preferably 50 to 90%.
- the ratio of the single Zn phase on the surface of the plating layer is less than 50%, the occupancy of the single phase of Zn on the surface of the plating layer is insufficient, and adhesion to the adhesive by the MgO-based oxide may deteriorate.
- the upper limit of the ratio of Zn single phases on the surface of the plating layer in the present invention, the greater the ratio of Zn single phases, the more improved adhesion with the adhesive. Therefore, the upper limit may not be separately limited.
- the proportion of Zn single phase on the surface of the plating layer may be 90% or less.
- the lower limit of the ratio of the Zn single phase on the surface of the plating layer may be 60%, or the upper limit of the ratio of the single phase of Zn on the surface of the plating layer may be 81%.
- the average diameter of the Zn single phase on the surface of the plating layer is preferably 3 ⁇ 20 ⁇ m.
- the average diameter of the Zn single phase on the surface of the plating layer is less than 3 ⁇ m, the effect of improving the adhesion may be insufficient, and when the average diameter of the Zn single phase exceeds 20 ⁇ m, there is a risk of lowering corrosion resistance.
- most of the Zn single phases on the surface of the plating layer may have a spherical or elliptical shape.
- the spherical or oval shape does not mean only the perfect spherical shape and oval shape, and also does not mean that the shape of all Zn single phases on the surface of the plating layer is a spherical or elliptical shape.
- it may mean that 80% or more of a phase having a ratio of the longest diameter to the shortest diameter of 0.8 to 1.2 is included.
- the ratio of the Zn-MgZn 2 phase on the surface of the plating layer may be controlled to be 10% or less (including 0%) as an area fraction.
- the Zn-MgZn 2 phase which is a binary process structure on the surface of the plating layer, may act as a factor to deteriorate the adhesion to the adhesive due to its characteristic wrinkles. Therefore, in the present invention, by controlling the ratio of the Zn-MgZn 2 phase to 10% or less on the surface of the plating layer, the adhesion to the adhesive can be further improved.
- the ratio of the Zn-MgZn 2 phase on the surface of the plating layer may be 1% or more.
- the ratio of the Zn-MgZn 2 -Al phase on the surface of the plating layer, as an area fraction may be 10 to 40%.
- the present inventors are not particularly limited, as a result of earnestly examining the factors affecting the adhesion to the adhesive resulting from the microstructure of the surface of the plating layer, the ratio of Zn-MgZn 2 -Al phase, which is a ternary eutectic structure, on the surface of the plating layer is It was found that it is more preferable to control the area fraction in an appropriate range.
- the ratio of the Zn-MgZn 2 -Al phase when the ratio of the Zn-MgZn 2 -Al phase is less than 10%, the ratio of the Zn-MgZn 2 phase on the surface of the plating layer becomes too large, which may cause a problem in that the sealer adhesion is poor.
- the ratio of the Zn-MgZn 2 -Al phase exceeds 40%, the ratio of the single Zn phase to the Zn-MgZn 2 -Al phase on the surface of the plating layer is insufficient, so the desired level of sealer adhesion is expected. Difficult problems may arise.
- the ratio of the area of the Zn-MgZn 2 phase to the area of the Zn-MgZn 2 -Al phase on the surface of the plating layer may be 1 to 4, more preferably 1.2 to 4.
- the microstructure on the surface of the plating layer may affect not only the ratio and size of the Zn single phase, but also binary and ternary eutectic structures, in the present invention, the ratio of binary and ternary eutectic structures is set within an appropriate range. It was confirmed that it is possible to further improve the sealer adhesion in addition to the corrosion resistance desired in the present invention by controlling the
- the plated layer of the plated steel sheet according to one aspect of the present invention is columnar (pillar shape) based on a cross section in the thickness direction (meaning a direction perpendicular to the rolling direction of the steel sheet) It may include a Zn single phase grown in the shape.
- the Zn single phase grown in the columnar shape refers to a Zn single phase that is in contact with the surface line of the plating layer but does not contact the interface line between the plating layer and the suppression layer.
- the ratio (Wa/Wb) of the maximum size (Wa) measured in the direction perpendicular to the rolling direction of the steel sheet and the length (Wb) of the Zn single phase occupying the surface line of the plating layer exceeds 1.0 (preferably at least 1.02) , more preferably 1.2 or more) may mean a single Zn phase.
- 50% or more of the Zn single phase in the plating layer may satisfy the above-described columnar shape. However, this does not mean that all Zn single phases grow in the form of columnar crystals.
- a Zn single phase in contact with the plating layer surface line, but not in contact with the interface line between the plating layer and the suppression layer, in the thickness direction of the Zn single phase in the thickness direction of the Zn single phase
- the ratio (Wa/Wb) of the maximum length (Wa) of the Zn single phase to the length (Wb) at which the Zn single phase occupies the surface line of the plating layer is greater than 1.0 may be 50% or more.
- the Zn single phase is evenly distributed throughout the thickness direction of the plating layer, and the binary and ternary eutectic structures are distributed with a uniform distribution between each Zn single phase.
- a desired surface quality may exhibit uniform characteristics, thereby ensuring uniformity of quality.
- the base iron may be annealed at a temperature of 800° C. or higher (more preferably 800° C. or higher and 850° C. or lower). If the annealing heat treatment temperature does not meet the temperature range, a problem of material hardening may occur.
- the annealing heat treatment of the base iron from 800 °C to 600 °C (that is, in the temperature range of 800 °C ⁇ 600 °C) at an average cooling rate of 2 ⁇ 5 °C / s cool down
- the cooling rate of the base iron before plating it is possible to uniformly control the structure of the base layer.
- the lower limit of the average cooling rate may be 4.3 °C / s, or in the primary cooling, the upper limit of the average cooling rate may be 5.0 °C / s have.
- the primary cooled base iron is heated from 600 ° C. to the plating bath temperature (that is, from 600 ° C. to the plating bath temperature (that is, the same temperature as the plating bath temperature) ° C.
- secondary cooling is performed at an average cooling rate of 25°C/s.
- the rapid cooling of the surface layer of the substrate may include a process of densely forming a fine-sized ferrite phase on the surface of the substrate.
- the lower limit of the average cooling rate may be 18 °C / s, or in the secondary cooling, the upper limit of the average cooling rate is 20 °C / S can
- Hot-dip galvanizing is performed by immersing in a plating bath containing the secondary cooled base iron in weight %, Mg: 1.0-2.0%, Al: 1.0-3.0%, the remainder Zn and other unavoidable impurities.
- the description of the plating layer of the plated steel sheet described above is equally applied.
- a composite ingot containing predetermined Zn, Al, or Mg or a Zn-Mg or Zn-Al ingot containing individual components may be used to prepare a plating bath having the above-described composition.
- the description of the plating layer described above can be applied in the same way except for Fe flowing from the base iron.
- the ingot is additionally melted and supplied.
- a method of dissolving the ingot by immersion directly in the plating bath may be adopted, or a method of dissolving the ingot in a separate pot and then replenishing the molten metal into the plating bath may be adopted.
- the optimum temperature for melting the ingot is 440 to 520 ° C.
- the higher the plating bath temperature the more it is possible to secure fluidity in the plating bath and form a uniform composition, and it is possible to reduce the amount of floating dross.
- the plating bath temperature is less than 440° C., the dissolution of the ingot is very slow, and the plating bath has a high viscosity, so it is difficult to secure excellent surface quality of the plating layer.
- the plating bath temperature exceeds 520°C, it is inappropriate to cause ash defects on the plating surface due to Zn evaporation.
- it is necessary to prepare the plating product by maintaining the temperature of the initial plating bath at about 500-520°C to proceed with dissolution, and then completing the plating bath stabilization at 440-480°C.
- a normal plating bath temperature may be applied as the temperature of the plating bath.
- the content of Al in the plating bath increases, so the melting point increases, so the equipment inside the plating bath is eroded and the equipment life is shortened. have.
- the Al content is controlled to be relatively low at 1.0 to 3.0 wt%, it is not necessary to set the temperature of the plating bath high, and in the present invention, it may be, for example, 440 to 480 °C.
- the lower limit of the temperature of the plating bath may be 450°C, or the upper limit of the temperature of the plating bath may be 470°C.
- the immersion time of the plating bath may be controlled in the range of 2 to 5 seconds, and the line speed may be 1 to 3 m/s.
- the gas wiping process is for adjusting the plating adhesion amount, and the method is not particularly limited.
- the gas used air, nitrogen, or argon may be used, and among these, nitrogen is more preferable from the viewpoint of economical efficiency and quality. This may cause surface defects of the plating layer by preferentially occurring Mg oxidation on the surface of the plating layer when air is used, and cost is high when using argon.
- the step of can do.
- gas wiping treatment to satisfy this, a beautiful surface free from oxidation defects can be obtained.
- the lower limit of the adhesion amount of the plating layer on one side may be 120 g/m 2
- the upper limit of the amount of adhesion on one side of the plating layer may be 150 g/m 2 .
- tertiary cooling in which a steel sheet having a hot-dip galvanized layer formed on its surface is taken out from the plating bath and cooled at an average cooling rate of 6 to 20° C./s from 460° C. or less (that is, in a temperature range of 460° C. to 300° C.) carry out
- the cooling end temperature is not particularly limited, and may be based on normal cooling conditions.
- the cooling method is not particularly limited, and for example, cooling may be performed by using an air jet cooler or by spraying N 2 wiping or water fog.
- the lower limit of the average cooling rate may be 10 °C / s (more preferably, 15 °C / s), or during the tertiary cooling,
- the upper limit of the average cooling rate may be 19° C./s.
- the base steel sheet was immersed in acetone and ultrasonically cleaned to remove foreign substances such as rolling oil remaining on the surface. Thereafter, after performing heat treatment in a reducing atmosphere at 800° C.
- a plating bath having the composition shown in Table 1 below (plating bath temperature: 460° C.) was immersed in base iron to perform plating, and then cooled to prepare a plated steel sheet. Then, the zinc alloy plating By gas wiping the steel, the plating adhesion amount was adjusted to 140 g/m 2 per side.
- the tertiary cooling was performed after the plating bath was introduced.
- the first cooling was performed, and then the secondary cooling was performed after the introduction into the plating bath.
- the plating layer was dissolved in a hydrochloric acid solution, and the dissolved liquid was analyzed by wet analysis (ICP) to measure the content (wt%) of each component, which is shown in Table 2 below.
- each manufactured plated steel sheet was observed with an FE-SEM (Field Emission-Scanning Electron Microscope, SUPRA-55VP, ZEISS) image, and then the surface fraction of Zn single phase and the long axis of the cross-sectional structure were used through an image analysis system (Analyser). The diameter was measured.
- FE-SEM analysis of the single-sided plating layer the distribution of Zn single phase in the plating layer and the columnar phase were observed.
- the columnar crystal was defined as a Zn single phase having a larger length in the thickness direction of the plating layer than the surface of the Zn single phase.
- FIG. 2 shows a 700 times FE-SEM image of the plating layer surface of Inventive Example 1
- FIG. 3 shows an FE-SEM image of 700 times the plating layer surface of Comparative Example 1.
- FIG. 4 shows a 1000-fold FE-SEM image of a cross-section of the plating layer of Inventive Example 1
- FIG. 5 shows a 1000-fold FE-SEM image of a cross-section of the plating layer of Comparative Example 1.
- the grade according to the evaluation criteria of adhesiveness is as follows.
- Table 2 expresses the percentage of surface Zn single phase structure (%), average particle diameter ( ⁇ m) of surface Zn single phase structure, lab shear test result (grade), and lab shear tensile strength (MPa) as the result.
- Comparative Examples 1 to 12 which did not satisfy at least one of the plating layer composition and manufacturing conditions of the present invention, at least one of the Lab Shear Test grade and Lab shear tensile strength was low, confirming that the adhesion with the adhesive was poor. .
- Plating layer composition (wt%, balance Zn) plating layer surface plating layer cross section uniformity Lab Shear Test Rating Lab shear Seal burglar (MPa) note No Mg Al Mg/Al Zn single phase Area rate (%) Zn single phase surface Average diameter size ( ⁇ m)
- Columnar crystals in the plating layer of Zn single phase include Whether A 1.2 1.8 0.67 81 3 ⁇ ⁇ 5 25.2 Invention Example 5 B 1.8 2.0 0.72 78 4 ⁇ ⁇ 5 24.3 Invention example 6 C 2.0 2.5 0.80 70 5 ⁇ ⁇ 5 21.0 Invention Example 7 D 1.3 1.5 0.87 65 6 ⁇ ⁇ 5 19.6 Invention Example 8 E 1.4 1.6 0.88 60 10 ⁇ ⁇ 5 19.2 Invention Example 9 F 1.8 2.0 0.94 41 12 X X 3 17.6 Comparative Example 9 G 1.6 1.6 1.00 30 10 X X 2 6.5 Comparative Example 10 H 1.8 1.4 1.29 21 12 X X 2 5.7 Comparative Example 11 I 1.7 1.2 1.42 12 8
- the ratio of the Zn-MgZn 2 phase on the surface of the plating layer is 10% or less as an area fraction
- the ratio of the Zn-MgZn 2 -Al phase on the surface of the plating layer is 10 to 40% as an area fraction
- the ratio of the area of the Zn-MgZn 2 phase to the area of the Zn-MgZn 2 -Al phase on the surface of the plating layer was 1.2-4.
- Comparative Examples 9 to 12 which did not satisfy at least one of the composition and manufacturing conditions of the plating layer of the present invention, at least one of the Lab Shear Test grade and Lab shear tensile strength was low, so the adhesion with the adhesive was inferior, and plating cracks Gender was also confirmed to be inferior.
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Abstract
Description
No | 도금욕 조성 (중량%) |
도금 전 | 도금 후 | 비고 | ||
Mg | Al | 1차 평균 냉각 속도 (800→600℃) |
2차 평균 냉각 속도 (600→460℃) |
3차 평균 냉각 속도 (460→300℃) |
||
1 | 1.2 | 1.6 | 5 | 20 | 17 | 발명예 1 |
2 | 1.2 | 1.6 | 5 | 17 | 14 | 발명예 2 |
3 | 1.2 | 1.6 | 4 | 15 | 12 | 발명예 3 |
4 | 1.2 | 1.6 | 3 | 12 | 10 | 발명예 4 |
5 | 1.2 | 1.6 | 5 | - | 8 | 비교예 1 |
6 | 1.2 | 1.6 | 3 | - | 10 | 비교예 2 |
7 | 1.2 | 1.6 | 4 | - | 13 | 비교예 3 |
8 | 1.2 | 1.6 | 5 | - | 17 | 비교예 4 |
9 | 1.2 | 1.6 | 5 | 8 | 8 | 비교예 5 |
10 | 1.2 | 1.6 | 3 | 11 | 10 | 비교예 6 |
11 | 1.2 | 1.6 | 4 | 12 | 4 | 비교예 7 |
12 | 1.2 | 1.6 | 4 | 13 | 5 | 비교예 8 |
No | 도금층 조성(wt%, 잔부 Zn) |
Zn 단상의 면적율 (%) | Zn 단상의 표면평균 직경 크기 (㎛) | Zn단상의 도금층내 주상정 포함 여부 |
Lab Shear Test 등급 | Lab shear 인장 강도 |
비고 | |
Mg | Al | |||||||
1 | 1.2 | 1.6 | 72 | 7 | O | 5 | 21.2 | 발명예 1 |
2 | 1.2 | 1.6 | 68 | 9 | O | 5 | 20.8 | 발명예 2 |
3 | 1.2 | 1.6 | 62 | 10 | O | 5 | 19.4 | 발명예 3 |
4 | 1.2 | 1.6 | 50 | 15 | O | 5 | 18.2 | 발명예 4 |
5 | 1.2 | 1.6 | 35 | 30 | X | 1 | 2.0 | 비교예 1 |
6 | 1.2 | 1.6 | 38 | 19 | X | 2 | 5.0 | 비교예 2 |
7 | 1.2 | 1.6 | 39 | 18 | X | 2 | 5.0 | 비교예 3 |
8 | 1.2 | 1.6 | 40 | 23 | X | 2 | 7.0 | 비교예 4 |
9 | 1.2 | 1.6 | 42 | 25 | X | 2 | 7.2 | 비교예 5 |
10 | 1.2 | 1.6 | 48 | 18 | X | 4 | 14.8 | 비교예 6 |
11 | 1.2 | 1.6 | 53 | 2 | X | 4 | 6.8 | 비교예 7 |
12 | 1.2 | 1.6 | 52 | 23 | X | 3 | 15.0 | 비교예 8 |
No. | 도금욕 조성 (중량%) | Mg/Al | 도금전 | 도금 후 | 비고 | ||
Mg | Al | 1차 평균 냉각 속도 (800→600℃) |
2차 평균 냉각 속도 (600→460℃) |
3차 평균 냉각 속도 (460→300℃) |
|||
A | 1.2 | 1.8 | 0.67 | 5 | 20 | 17 | 발명예 5 |
B | 1.8 | 2.0 | 0.72 | 5 | 20 | 17 | 발명예 6 |
C | 2.0 | 2.5 | 0.80 | 5 | 20 | 17 | 발명예 7 |
D | 1.3 | 1.5 | 0.87 | 5 | 20 | 17 | 발명예 8 |
E | 1.4 | 1.6 | 0.88 | 5 | 20 | 17 | 발명예 9 |
F | 1.8 | 2.0 | 0.94 | 5 | 20 | 17 | 비교예 9 |
G | 1.6 | 1.6 | 1.00 | 5 | 20 | 17 | 비교예 10 |
H | 1.8 | 1.4 | 1.29 | 5 | 20 | 17 | 비교예 11 |
I | 1.7 | 1.2 | 1.42 | 5 | 20 | 17 | 비교예 12 |
도금층 조성 (wt%, 잔부 Zn) | 도금층 표면 | 도금층 단면 | 균일성 | Lab Shear Test 등급 |
Lab shear 인장 강도 (MPa) |
비고 | ||||
No | Mg | Al | Mg/Al | Zn 단상의 면적율 (%) |
Zn단상의 표면 평균 직경 크기 (㎛) |
Zn단상의 도금층내 주상정 포함 여부 |
||||
A | 1.2 | 1.8 | 0.67 | 81 | 3 | ○ | ○ | 5 | 25.2 | 발명예 5 |
B | 1.8 | 2.0 | 0.72 | 78 | 4 | ○ | ○ | 5 | 24.3 | 발명예 6 |
C | 2.0 | 2.5 | 0.80 | 70 | 5 | ○ | ○ | 5 | 21.0 | 발명예 7 |
D | 1.3 | 1.5 | 0.87 | 65 | 6 | ○ | ○ | 5 | 19.6 | 발명예 8 |
E | 1.4 | 1.6 | 0.88 | 60 | 10 | ○ | ○ | 5 | 19.2 | 발명예 9 |
F | 1.8 | 2.0 | 0.94 | 41 | 12 | X | X | 3 | 17.6 | 비교예 9 |
G | 1.6 | 1.6 | 1.00 | 30 | 10 | X | X | 2 | 6.5 | 비교예 10 |
H | 1.8 | 1.4 | 1.29 | 21 | 12 | X | X | 2 | 5.7 | 비교예 11 |
I | 1.7 | 1.2 | 1.42 | 12 | 8 | X | X | 1 | 1.6 | 비교예 12 |
Claims (8)
- 소지철;상기 소지철 상의 적어도 일면에 구비된 Zn-Mg-Al계 도금층; 및상기 소지철과 상기 Zn-Mg-Al계 도금층 사이에 구비된 Fe-Al계 억제층;을 포함하고,상기 도금층은 중량%로, Mg: 1.0~2.0%, Al: 1.0~3.0%, 잔부 Zn 및 기타 불가피한 불순물을 포함하고,상기 도금층 표면에서 Zn 단상의 비율은 면적분율로, 50% 이상이고,상기 도금층 표면에서 Zn 단상의 평균 직경은 3~20㎛인, 도금 강판.
- 청구항 1에 있어서,상기 도금층 표면에서 Zn-MgZn2상의 비율은 면적분율로, 10% 이하(0% 포함)인, 도금 강판.
- 청구항 1에 있어서,상기 도금층 표면에서 Zn-MgZn2-Al상의 비율은 면적분율로, 10~40%인, 도금 강판.
- 청구항 1에 있어서,상기 도금층 표면에서 Zn-MgZn2상의 면적과 Zn-MgZn2-Al상의 면적의 비율은 1~4인, 도금 강판.
- 청구항 1에 있어서,상기 도금층은 두께방향 단면을 기준으로, 도금층 표면선에 접촉하되, 도금층과 억제층 사이의 계면선에 접촉하지 않는 Zn 단상으로서, 상기 Zn 단상의 두께방향으로의 최대 길이(Wa)와 상기 Zn 단상이 도금층 표면을 점유하는 길이(Wa)의 비율(Wa/Wb)이 1.0을 초과하는 Zn 단상을 포함하는, 도금 강판.
- 소지철을 준비한 후, 800℃ 이상의 온도로 소둔 열처리하는 단계;상기 소둔 열처리된 소지철을 800℃에서 600℃까지 2~5℃/s의 평균 냉각 속도로 1차 냉각하는 단계;상기 1차 냉각된 소지철을 600℃에서 도금욕 온도까지 13~25℃/s의 평균 냉각 속도로 2차 냉각하는 단계;2차 냉각된 소지철을 중량%로, Mg: 1.0~2.0%, Al: 1.0~3.0%, 잔부 Zn 및 기타 불가피한 불순물을 포함하는 도금욕에 침지하여 용융 아연도금하는 단계; 및상기 용융아연 도금 후, 도금욕 탕면에서부터 냉각을 개시하여 탑 롤 구간까지 6~20℃/s의 평균 냉각 속도로 냉각하는 단계;를 포함하는, 도금 강판의 제조방법.
- 청구항 6에 있어서,상기 용융 아연도금하는 단계는 도금욕의 침지 시간을 2~5초 범위로 제어하고, 강판의 라인 스피드가 1~3m/s 범위가 되도록 제어하며,상기 용융 아연도금 후, 질소 가스를 이용하여 도금층 편면 부착량을 35~200g/m2 범위가 되도록, 에어 와이핑하는 단계를 더 포함하는, 도금 강판의 제조방법.
- 청구항 6에 있어서,상기 도금욕의 온도는 440~480℃ 범위로 제어하는, 도금 강판의 제조방법.
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