WO2022245064A1 - 내수소취성이 우수한 열간성형용 도금강판, 열간성형 부재 및 이들의 제조방법 - Google Patents
내수소취성이 우수한 열간성형용 도금강판, 열간성형 부재 및 이들의 제조방법 Download PDFInfo
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- WO2022245064A1 WO2022245064A1 PCT/KR2022/006922 KR2022006922W WO2022245064A1 WO 2022245064 A1 WO2022245064 A1 WO 2022245064A1 KR 2022006922 W KR2022006922 W KR 2022006922W WO 2022245064 A1 WO2022245064 A1 WO 2022245064A1
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- steel sheet
- hot
- hydrogen embrittlement
- embrittlement resistance
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 110
- 239000010959 steel Substances 0.000 title claims abstract description 110
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
Definitions
- the present invention relates to a coated steel sheet for hot press forming (HPF) used as automobile body parts, a hot-formed member, and a method for manufacturing the same.
- HPF hot press forming
- hot-formed members have been widely used in structural members such as automobiles for the purpose of improving fuel efficiency and protecting passengers through weight reduction of automobiles.
- a plated steel sheet having a plated surface is often used in order to secure corrosion resistance and the like.
- Patent Document 1 As a representative technique related to such hot forming technology.
- Patent Document 1 after heating an Al-Si plated steel sheet to 850° C. or more, the structure of a member by hot forming and rapid cooling by a press is formed into martensite, so that ultra-high strength can be secured.
- ultra-high strength is secured using such a hot forming technology, complex shapes can be easily formed because molding is performed at a high temperature.
- high-strength and lightweight effects can be expected at the same time.
- the martensitic structure is known to have low resistance to hydrogen embrittlement.
- parts manufactured after hot forming have residual stress due to rapid cooling after heating and when the amount of diffusible hydrogen in steel increases, delayed fracture due to hydrogen embrittlement may occur, so the application of parts is limited. . Therefore, there is a demand for a method for solving this problem.
- Patent Document 1 US Patent Registration No. 6296805
- One aspect of the present invention relates to a coated steel sheet for hot forming having excellent hydrogen embrittlement resistance by reducing the occurrence of delayed fracture due to hydrogen embrittlement of a hot formed member, a hot formed member manufactured using the same, and a method for manufacturing them. will be.
- One aspect of the present invention is a holding steel plate
- An average content of Ni in the Al-based plating layer is about 0.05 to 0.35% by weight, and relates to a coated steel sheet for hot forming having excellent hydrogen embrittlement resistance.
- Another aspect of the present invention comprises the steps of preparing a holding steel sheet
- It relates to a method for manufacturing a coated steel sheet for hot forming having excellent hydrogen embrittlement resistance.
- Another aspect of the present invention is So Ji-cheol.
- It relates to a hot-formed member having excellent hydrogen embrittlement resistance, wherein the Ni content is 0.1 to 0.75% by weight at the point where the Ni content is highest (Nimax) from the surface of the alloy plating layer to 15 ⁇ m in the depth direction.
- Another aspect of the present invention provides a blank comprising a base steel sheet and an Al-based plating layer formed on a surface of the base steel sheet, wherein the average content of Ni in the Al-based plating layer is 0.05 to 0.35% by weight;
- It relates to a method for manufacturing a hot-formed member having excellent hydrogen embrittlement resistance.
- the amount of diffusible hydrogen in steel can be reduced, and a hot formed member excellent in hydrogen embrittlement resistance can be provided.
- Example 1 is a graph obtained by analyzing Fe and Ni contents of an Al-based plating layer in a plated steel sheet for hot forming of Inventive Example 1 among Examples by glow discharge optical emission spectrometry (GDS).
- GDS glow discharge optical emission spectrometry
- Figure 2 is a graph of GDS analysis of the Ni content in the alloy plating layer of the hot-formed member of Example 3 of Example 3, showing the Ni enriched layer through this.
- Figure 3 is a graph of GDS analysis of the Ni content in the alloy plating layer of the hot-formed members of Inventive Examples 1 to 3 and Comparative Example 2 among Examples.
- the inventors of the present invention found that during the step of heating a blank (manufactured from a plated steel sheet for hot-forming) having a plating layer of aluminum or the like during hot forming, the water vapor present in the heat treatment furnace adsorbed on the surface of the blank. Subsequently, hydrogen generated by dissociation of water is occluded in steel having an austenite phase with high hydrogen solubility at high temperatures.
- the inventors of the present invention discovered the effect that the amount of diffusible hydrogen can be reduced through Ni plating while analyzing the amount of diffusible hydrogen in steel that affects hydrogen embrittlement in steel for hot forming, and led to the present invention.
- a coated steel sheet for hot forming which is an aspect of the present invention, includes a base steel sheet and an Al-based plating layer formed on the base steel sheet, and the Ni content in the Al-based plating layer is preferably 0.05% by weight or more.
- the Al-based plating layer is sufficient to be an Al-based plating widely used in the coated steel sheet for hot forming performed by a person skilled in the art in the technical field of the coated steel sheet for hot forming to which the present invention belongs.
- the content or type is not particularly limited. For example, it can include not only pure Al plating, but also plating performed by partially including Si in Al.
- the Al-based plating layer may include an Al-rich layer and a concentration gradient layer.
- the concentration gradient layer is a section formed including Fe by mutual reaction between Fe of the steel sheet and components of the Al plating bath in the process of performing Al-based plating with the steel sheet. It is not easy to clearly distinguish the boundary between the Al-rich layer and the concentration gradient layer in the Al-based plating layer. However, the Fe content in the Al-rich layer is less than the Fe content in the concentration gradient layer.
- the content of Fe in the Al-based plating layer is about 2% by weight or more, it can be understood that the content of Fe diffused from the base steel sheet is greater than the plating component, so that the boundary between the Al-rich layer and the concentration gradient layer It can be considered, and the boundary between the concentration gradient layer and the base steel sheet can be seen as up to the point where the Fe content becomes approximately 80% by weight, but is not necessarily clearly distinguished therefrom.
- FIG. 1 is an analysis result obtained by performing glow discharge optical emission spectrometry (GDS) on the coated steel sheet for hot forming of Inventive Example 1 of the following Examples from the surface to the depth direction, through which It can be understood that the Al-based plating layer includes an Al-rich layer and a concentration gradient layer having an Fe content of up to 80% by weight.
- GDS glow discharge optical emission spectrometry
- the Al-based plating layer preferably includes an average Ni content of 0.05% by weight or more.
- Ni included in the Al-based plating layer is preferably distributed in a depth direction.
- the content of Ni is not constant from the surface of the plated steel sheet to the depth of the plated layer.
- the average content means the average of the results of analysis from the surface to the depth of the Al-based plating layer. As a preferred example of measuring this, it can be derived as the average value of the graph in the GDS analysis Ni profile as shown in FIG.
- Ni included in the Al-based plating layer promotes the formation of a Ni-enriched layer in the alloy plating layer formed in the hot forming process, and the Ni-enriched layer formed in this way is external hydrogen that can be occluded during the heat treatment process for hot forming. It serves to prevent penetration of the steel sheet. Through this, it serves to improve the hydrogen embrittlement resistance of the hot-formed member.
- Ni content When the Ni content is less than 0.05% by weight, a sufficient Ni-enriched layer is not formed during hot forming, and accordingly, it is difficult to effectively prevent external hydrogen occluded during the hot forming heat treatment.
- the higher the Ni content the higher the effect of blocking external hydrogen.
- the Ni content exceeds 0.35% by weight, it is difficult to manufacture a homogeneous steel sheet due to an increase in cost and non-uniformity in the width direction due to an increase in Ni adhesion amount, so that the Ni content does not exceed 0.35% by weight. desirable.
- a more preferable range is 0.055 to 0.335% by weight.
- the type of the base steel sheet and the composition of the alloy are not particularly limited, and any type can be used as a hot-formed member.
- the steel sheet contains, by weight, carbon (C): 0.07-0.5%, silicon (Si): 0.05-1%, manganese (Mn): 0.5-4%, phosphorus (P): 0.001 ⁇ 0.015%, Sulfur (S): 0.0001 ⁇ 0.02%, Aluminum (Al): 0.01 ⁇ 0.1%, Chromium (Cr): 0.01 ⁇ 1%, Nitrogen (N): 0.001 ⁇ 0.02% ) and unavoidable impurities. Additionally, titanium (Ti): 0.1% or less (including 0), boron (B): 0.01% or less (including 0) may be included.
- each alloy component is briefly described.
- C is an element that improves the strength and hardenability of the hot-formed member, and should be appropriately included as an essential element for strength control. If the C content is less than 0.07%, the hardenability is low, so that sufficient martensite cannot be secured when the cooling rate is reduced, and it is difficult to secure the desired strength by generating ferrite, so it is preferable to include 0.07% or more. Since it rises excessively, causes brittleness, and deteriorates weldability, it is preferable not to exceed 0.5%.
- the Si should be added as a deoxidizing agent in steelmaking, as well as being a solid solution strengthening element, suppressing carbide formation, and being effective in uniformizing the internal structure. In addition, it contributes to the increase in the strength of hot-formed members and is an effective element for material uniformity. However, if the content is less than 0.05%, it is difficult to expect the above effect, and if the content exceeds 1%, plating properties are greatly reduced due to excessive Si oxide generated on the surface of the steel sheet during annealing, so it is preferably 1% or less.
- the Mn is an element necessary for securing desired strength due to the solid solution strengthening effect and suppressing formation of ferrite during hot forming through improvement of hardenability.
- the Mn content is less than 0.5%, it is difficult to obtain a sufficient hardenability effect, and an excessive amount of other expensive alloy elements are required for insufficient hardenability, resulting in a significant increase in manufacturing cost.
- the Mn content exceeds 4%, the band-like structure arranged in the rolling direction on the microstructure deepens, causing non-uniformity of the internal structure, which can lead to inferior crash resistance. desirable.
- the P exists as an impurity in steel and is undesirable because high manufacturing costs are required for the minimum content of less than 0.001%, and when the maximum content exceeds 0.015%, the material properties due to the weldability of hot-formed members and high-temperature grain boundary segregation Since this deteriorates, it is preferable not to exceed 0.015%.
- the S is an impurity, and since it is an element that impairs the ductility, impact characteristics and weldability of the member, it is preferable to set the maximum content to 0.02%. In addition, in order to make the minimum content less than 0.0001%, it is not preferable because the manufacturing cost greatly increases.
- the Al is an element that, together with Si, acts as a deoxidizer in steelmaking to increase the cleanliness of the steel. If the Al content is less than 0.01%, it is difficult to obtain this effect, and if it exceeds 0.1%, high-temperature ductility is lowered due to excessive AlN precipitates formed during the casting process, and slab cracks may occur, causing manufacturing problems. is preferably 0.1%.
- Cr like Mn
- Cr is added as an element for securing hardenability of steel and suppressing the generation of ferrite after hot forming. If the Cr content is less than 0.01%, it is difficult to secure the above effect, and if the Cr content exceeds 1%, the effect of improving the hardenability compared to the amount added is insignificant, and coarse iron carbides are excessively formed, which can cause cracks during stress. It is preferable not to exceed 1% because it may cause inferiority.
- the N is included as an impurity in steel. If the N content is less than 0.001%, excessive manufacturing costs are involved, and if the content exceeds 0.02%, slab cracks due to AlN formation, such as added Al, are likely to occur, so it is preferable not to exceed 0.02%.
- the Ti is combined with nitrogen remaining as an impurity in the steel to form TiN, so that B for securing hardenability can be protected from becoming a compound.
- Ti may be additionally included.
- TiC precipitates, precipitation strengthening and crystal grain refinement effects can be expected.
- the content exceeds 0.1%, a large amount of coarse TiN is formed, which deteriorates the quality of the steel, so it is preferable that the upper limit does not exceed 0.1%.
- B is an element that can effectively improve hardenability, and can be additionally included because it is segregated at the prior austenite grain boundary and suppresses brittleness of the hot-formed member due to grain boundary segregation of impurities P and / or S.
- the B content exceeds 0.01%, the Fe 23 CB 6 composite compound may be formed and brittleness may be caused in hot rolling, so the upper limit is preferably 0.01%.
- the remainder includes iron (Fe) and unavoidable impurities.
- Fe iron
- Inevitable impurities can be unintentionally mixed in the normal steel manufacturing process, and cannot be completely excluded, and those skilled in the ordinary steel manufacturing field can easily understand the meaning.
- the present invention does not entirely exclude the addition of other compositions than the aforementioned steel composition.
- the described manufacturing method is a preferred example of manufacturing the above-described coated steel sheet for hot forming, and does not necessarily have to be manufactured therefrom.
- the manufacturing method includes preparing a holding steel sheet; Ni-plating the surface of the prepared base steel sheet; and continuously annealing the Ni-plated base steel sheet and performing Al-based plating.
- the base steel sheet is as described above, and the process of preparing the base steel plate may be obtained by heating a steel slab satisfying the above-described toughness, followed by hot rolling, winding, or cold rolling.
- a steel slab satisfying the above composition is heated to 1050 to 1300° C. and then hot-rolled. If the heating temperature is less than 1050 ° C, the steel slab structure is not sufficiently homogenized, so it is difficult to re-dissolve when using precipitated elements, and if it exceeds 1300 ° C, an excessive oxide layer is formed, resulting in an increase in manufacturing cost for removing the oxide layer, After rolling, the possibility of occurrence of surface defects increases.
- the finish rolling temperature of the hot rolling is preferably performed in a temperature range of 800 to 950 ° C.
- the finish rolling temperature is less than 800° C.
- abnormal reverse rolling proceeds, and ferrite is introduced into the surface layer portion of the steel sheet, making it difficult to control the plate shape.
- the temperature exceeds 950 ° C., coarsening of hot-rolled grains may occur.
- a cold rolling process is performed.
- a pickling process may be further performed to remove surface oxides before cold rolling. If necessary, it can be used as a holding steel sheet for hot forming by performing plating without performing cold rolling.
- the cold rolling reduction rate during the cold rolling is performed to obtain a predetermined thickness, and is preferably performed at a reduction rate of 30 to 80%.
- Ni plating is performed on the surface of the base steel sheet prepared as described above.
- Ni flash plating may be performed.
- Ni flash plating is one of a kind of electroplating method performed before annealing, and is performed by adjusting the amount of current or the like between electroplating using Ni electrolyte.
- the Ni plating is preferably performed in an amount of 150 to 2500 mg/m 2 on the surface of the base steel sheet.
- the Ni plating adhesion amount performed by the said Ni plating is 150-2500 mg/m ⁇ 2>. If the amount of Ni plating is less than 150 mg/m 2 , the effect of the present invention cannot be sufficiently exhibited because Ni is not concentrated in the plating layer in the heat treatment for hot forming, and if the Ni plating amount exceeds 2500 mg/m 2 , excessive current concentration during electroplating As a result, not only local non-plating occurs inside the steel sheet, but also excessive use of electroplating solution for Ni coating, etc., excessively increases manufacturing cost, so it is preferable to carry out at 2500 mg / m 2 or less. On the other hand, as for the more preferable Ni plating adhesion amount, 200-2000 mg/m ⁇ 2> is preferable.
- the Ni-plated base steel sheet is continuously annealed and subjected to Al-based plating.
- the annealing temperature during the annealing is preferably 740 ⁇ 860 °C. If the annealing temperature is less than 740 ° C., recrystallization of the cold-rolled structure is not sufficiently completed, and thus the plate shape may be poor, and the strength after plating may be too high, causing mold wear during the blanking process. On the other hand, when the temperature exceeds 860 ° C., surface oxide formation is promoted during the annealing process, which may cause defects on the plating surface during Al-based plating.
- the atmosphere during the annealing heat treatment is preferably a non-oxidizing atmosphere, and a hydrogen-nitrogen mixed gas or the like can be used.
- the dew point temperature of the atmosphere gas is -75 to -20°C.
- additional facilities for controlling the dew point temperature are required, so there is a problem of increasing manufacturing cost, and when it exceeds -20 ° C, annealed oxide is formed on the surface of the steel sheet during annealing, resulting in unplating. surface quality defects.
- Al-based plating refers to aluminum or aluminum alloy plating, and any plating layer applied to a plated steel sheet for hot forming may be applied to the present invention without limitation.
- the Al-based plating is preferably performed by being immersed in an Al-based plating bath.
- the plating bath composition is silicon (Si): 6 to 12% by weight, iron (Fe): 1 to 4% by weight, and the rest is It is preferable to include aluminum (Al) and unavoidable impurities.
- the coating weight it is preferable to set the coating weight to 20 to 140 g/m2 based on one side. If the amount of plating on one side is less than 20 g/m 2 , it is difficult to secure the desired corrosion resistance of the hot-formed member. On the other hand, in the case of exceeding 140 g/m 2 , not only does manufacturing cost increase due to excessive coating weight, but it is not easy to uniformly plate the plating layer in the entire width and length direction of the coil.
- the hot-formed member may be obtained by hot-forming the above-described coated steel sheet for hot forming.
- the hot-formed member includes a base iron and an alloy plating layer formed on the base iron, and the alloy plated layer has a Ni content at the point where the Ni content is highest (Nimax) as a result of measuring the Ni content from the surface to 15 ⁇ m. It is preferable that silver is 0.1 weight % or more. As an example of a method of confirming Nimax, it can be confirmed by analyzing a graph obtained as a result of glow discharge optical emission spectrometry (GDS). If the Ni content in the Nimax is less than 0.1% by weight, the Ni enriched layer is not sufficiently formed, and thus the occlusion of external hydrogen during hot forming cannot be effectively prevented, making it difficult to secure hydrogen embrittlement resistance.
- GDS glow discharge optical emission spectrometry
- Ni content in Nimax the higher the effect of suppressing hydrogen occlusion, but if the content is excessive, there is a concern about an increase in cost due to an increase in the amount of Ni adhesion, and there is a concern that environmental problems may occur during welding, so 0.75% by weight It is desirable not to exceed
- the alloy plating layer is a layer obtained by alloying the Al-based plating layer by reacting with each other in the heating process by hot forming, and the alloy plating layer is not particularly limited in the present invention.
- Ni enriched layer it is preferable to include a Ni enriched layer in the alloy plating layer.
- a graph of a concentration profile derived using glow discharge optical emission spectrometry (GDS) may be used in the thickness direction of the member from the surface of the alloy plating layer.
- GDS glow discharge optical emission spectrometry
- a width between points Nio' having ? may be defined as the Ni enriched layer.
- FIG. 2 is a concentration profile graph obtained by GDS analysis of the Ni content in the hot-formed member of Inventive Example 3 among the following Examples.
- the Nimax, Nio, and Nio' are derived, and the Ni enriched layer can be confirmed from this.
- the thickness of the Ni enriched layer is not particularly limited and may vary depending on heat treatment conditions during plating and hot forming. As a specific example, the thickness of the Ni enriched layer is preferably 1 to 15 ⁇ m. If the thickness of the Ni-enriched layer is less than 1 ⁇ m, it is difficult to secure sufficient hydrogen embrittlement resistance, and if it exceeds 15 ⁇ m, excessive Ni flash plating must be performed, and cost increase and environmental problems during welding can be caused.
- the amount of diffusible hydrogen in the hot-formed member is preferably 0.3 ppm by weight or less.
- the amount of diffusible hydrogen of the hot-formed member can be measured using TDA (Thermal Desortion Analysis) equipment.
- the diffusion hydrogen curve was measured by maintaining the time to sufficiently appear, and it is a value obtained by integrating this curve.
- the base steel sheet of the coated steel sheet for hot forming and the base iron of the hot forming member do not have a large difference in alloy composition, but there may be a difference in microstructure, so it is preferable to distinguish them. Accordingly, in the present invention, the holding steel sheet is used in the plated steel sheet for hot forming, and the holding iron is distinguished in the hot forming member.
- the base steel sheet of the coated steel sheet for hot forming although ferrite and pearlite structures are formed, in the base iron of the hot formed member formed through hot forming, martensite is formed in the main phase and some bainite may be formed. .
- a method for manufacturing a hot-formed member which is another aspect of the present invention, will be described.
- a blank including a base steel sheet and an Al-based plating layer formed on a surface of the base steel sheet, wherein an average content of Ni in the Al-based plating layer is 0.05 to 0.35% by weight is provided.
- the blank may be manufactured using the above-described plated steel sheet for hot forming.
- the provided blank above the austenite single-phase temperature, more specifically in the temperature range of Ac3 to 975°C.
- the heating temperature is less than the Ac3 temperature, it is difficult to secure strength and crash resistance due to the existence of untransformed ferrite according to the ideal range.
- the heating temperature exceeds 975 ° C., excessive oxide is generated on the surface of the member, making it difficult to secure spot weldability, and manufacturing costs for maintaining a high temperature increase.
- the Ar3 can be derived by the following formula.
- Ar3 902-255C+19Si-11Mn-5Cr [°C]
- the heated blank is transferred to a press to form and cool.
- the cooling rate is preferably 20 °C / s or more.
- the cooling rate is less than 20° C./s, a ferrite phase is introduced during cooling and formed at grain boundaries, and physical properties such as strength and collision resistance may be deteriorated.
- the processes of transferring, forming and cooling the blank are not particularly limited, and those commonly used for the hot forming method may be applied as they are.
- a steel slab having a thickness of 60 mm satisfying the strength (unit is weight%) of Table 1 below was manufactured by vacuum melting. At this time, the rest of the emphasis not described in Table 1 is Fe and unavoidable impurities.
- the prepared steel slab was heated to 1200° C. and maintained for 1 hour, followed by hot rolling, finishing at a hot rolling end temperature of 900° C., and winding at a temperature of 600° C. Thereafter, cold rolling was performed to prepare a cold rolled steel sheet having a thickness of 1.5 mm.
- Ni plating was performed on the cold-rolled steel sheet through Ni flash treatment. At this time, the Ni coating weight adhesion amount is shown in Table 1.
- the Ni flash treatment was electroplating using Ni electrolyte, and the amount of adhesion was controlled by adjusting the amount of current during electroplating.
- the Ni flash-treated cold-rolled steel sheet was annealed, and an Al-based plating bath containing 9% by weight of Si, 2% by weight of Fe, and the rest Al and unavoidable impurities was used, the plating temperature was about 660 ° C, and the amount of plating was on one side. It was carried out with a standard of 75 g/m 2 .
- the continuous annealing was performed at a temperature of 800 °C.
- the average content of Ni distributed in the Al-based plating layer of the plated steel sheet prepared as above was measured and shown in Table 2.
- the Al-based plating layer was measured including the plating layer and the concentration gradient layer (up to the point where the Fe content in the Al-based plating layer is 80% by weight or less), using GDS850A (model name, product of LECO) DC and RF equipment and analyzed using glow discharge optical emission spectrometry (GDS).
- GDS850A model name, product of LECO
- the produced plated steel sheet was visually inspected to measure the length of the major axis of the peeled portion of the steel sheet, and evaluated according to the following criteria and is shown in Table 2.
- ⁇ The length of the major axis of the peeled site is 3 mm or less
- ⁇ The length of the major axis of the peeled area exceeds 3 mm
- a blank was prepared using the plated steel sheet, heated to 900° C., held for 6 minutes, transferred to a mold within 10 seconds, and molded and cooled. At this time, cooling was performed at a cooling rate of 20 to 40° C./s.
- the GDS analysis of the Ni content at the point where the Ni content was highest from the surface of the alloy plating layer to 15 ⁇ m in the depth direction (Nimax) was performed, and the results are shown in Table 2, and the diffusive number in the member A small amount was measured and similarly shown in Table 2.
- FIG. 1 is a graph obtained by GDS analysis of Fe and Ni contents in the Al-based plated layer of the coated steel sheet for hot forming of Example 1 above.
- 2 is a graph of GDS analysis of the Ni content in the alloy plating layer in the hot-formed members of Inventive Examples 1 to 3 and Comparative Example 2.
- 3 is a graph showing the maximum content of Ni and the amount of diffusible hydrogen in the alloy plating layer in the hot-formed members of Inventive Examples 1 to 8 and Comparative Examples 1 to 2.
- the inventive examples belonging to the scope of the present invention have excellent plating adhesion to coated steel sheets, and excellent hydrogen embrittlement resistance when hot-formed. It can be seen that it has
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Abstract
Description
강종 | C | Si | Mn | P | S | Al | Cr | N | Ti | B | Ni 부착량 (㎎/㎡) |
A | 0.218 | 0.31 | 1.1 | 0.012 | 0.001 | 0.028 | 0.19 | 0.0042 | 0.027 | 0.0026 | 300 |
B | 0.222 | 0.4 | 1.2 | 0.013 | 0.001 | 0.023 | 0.08 | 0.0035 | 0.029 | 0.0026 | 200 |
C | 0.105 | 0.26 | 1.6 | 0.01 | 0.001 | 0.034 | 0.4 | 0.0046 | 0.031 | 0.0027 | 500 |
D | 0.310 | 0.35 | 2.1 | 0.011 | 0.001 | 0.029 | 0.2 | 0.004 | 0.03 | 0.0025 | 400 |
E | 0.325 | 0.61 | 2.1 | 0.011 | 0.001 | 0.026 | 0.19 | 0.0049 | 0.031 | 0.0025 | 1000 |
F | 0.071 | 0.58 | 3.6 | 0.011 | 0.001 | 0.023 | 0.17 | 0.0053 | 0.032 | 0.0025 | 2000 |
G | 0.147 | 0.60 | 1.1 | 0.011 | 0.002 | 0.031 | 0.21 | 0.0041 | 0.027 | 0.003 | 800 |
H | 0.343 | 0.90 | 0.6 | 0.013 | 0.001 | 0.05 | 0.3 | 0.0043 | 0.029 | 0.0029 | 1500 |
I | 0.230 | 0.52 | 1.2 | 0.008 | 0.001 | 0.025 | 0.3 | 0.0047 | 0.025 | 0.0025 | 100 |
J | 0.208 | 0.31 | 1.2 | 0.009 | 0.002 | 0.033 | 0.31 | 0.0029 | 0.03 | 0.0026 | 10 |
K | 0.237 | 0.20 | 1.4 | 0.008 | 0.002 | 0.042 | 0.21 | 0.0027 | 0.028 | 0.0026 | 2550 |
L | 0.327 | 0.28 | 1.0 | 0.008 | 0.002 | 0.030 | 0.10 | 0.0027 | 0.028 | 0.0026 | 2700 |
구분 | 도금강판 도금층 내 Ni 평균 함량 (중량%) |
도금강판의 도금 밀착성 | 열간성형 부재 내 합금 도금층 표면에서 15㎛까지 최대 Ni 지점의 Ni 함량 (중량%) |
열간성형 부재 내 확산성 수소량 (ppm) |
비고 |
A | 0.112 | ○ | 0.123 | 0.2407 | 발명예 1 |
B | 0.055 | ○ | 0.104 | 0.2872 | 발명예 2 |
C | 0.186 | ○ | 0.251 | 0.1880 | 발명예 3 |
D | 0.153 | ○ | 0.208 | 0.2106 | 발명예 4 |
E | 0.264 | ○ | 0.359 | 0.1331 | 발명예 5 |
F | 0.335 | ○ | 0.734 | 0.1204 | 발명예 6 |
G | 0.207 | ○ | 0.316 | 0.1570 | 발명예 7 |
H | 0.306 | ○ | 0.503 | 0.1301 | 발명예 8 |
I | 0.037 | ○ | 0.065 | 0.3231 | 비교예 1 |
J | 0.001 | ○ | 0.003 | 0.3610 | 비교예 2 |
K | 0.393 | Х | 0.837 | 0.1116 | 비교예 3 |
L | 0.403 | Х | 0.861 | 0.1051 | 비교예 4 |
Claims (13)
- 소지강판; 및상기 소지강판 표면에 형성된 Al계 도금층을 포함하고,상기 Al계 도금층 내 Ni 평균 함량은 0.05~0.35 중량%인 내수소취성이 우수한 열간성형용 도금강판.
- 상기 청구항 1에 있어서,상기 소지강판은 중량%로, C: 0.07~0.5%, Si: 0.05~1%, Mn: 0.5~4%, P: 0.001~0.015%, S: 0.0001~0.02%, Al: 0.01~0.1%, Cr: 0.01~1%, N: 0.001~0.02%, Ti: 0.1% 이하, B: 0.01% 이하를 포함하고, 나머지는 Fe 및 불가피한 불순물을 포함하는 내수소취성이 우수한 열간성형용 도금강판.
- 상기 청구항 1에서상기 Al계 도금층은 Al-리치층과 농도구배층을 포함하는 내수소취성이 우수한 열간성형용 도금강판.
- 소지강판을 준비하는 단계;상기 준비된 소지강판을 도금 부착량 150~2500㎎/㎡로 Ni 도금하는 단계; 및상기 Ni 도금된 냉연강판을 연속소둔하고 Al계 도금하는 단계;를 포함하는 내수소취성이 우수한 열간성형용 도금강판의 제조방법.
- 청구항 4에 있어서,상기 소지강판을 준비하는 단계는,중량%로, C: 0.07~0.5%, Si: 0.05~1%, Mn: 0.5~4%, P: 0.001~0.015%, S: 0.0001~0.02%, Al: 0.01~0.1%, Cr: 0.01~1%, N: 0.001~0.02%, Ti: 0.1% 이하, B: 0.01% 이하를 포함하고, 나머지는 Fe 및 불가피한 불순물을 포함하는 강슬라브를 준비하는 단계;상기 강슬라브를 1050~1300℃로 가열하는 단계;상기 가열된 강슬라브를, 800~950℃의 온도범위에서 마무리 열간압연하여 열연강판을 제조하는 단계;상기 열연강판을 500~700℃의 온도범위에서 권취하는 단계; 및상기 권취 후 산세하고 30~80%의 압하율로 냉간압연하는 단계;를 포함하는 내수소취성이 우수한 열간성형용 도금강판의 제조방법.
- 청구항 4에 있어서,상기 연속소둔은 740~860℃의 온도범위, 이슬점 온도 -75~-25℃에서 행하는 내수소취성이 우수한 열간성형용 도금강판의 제조방법.
- 소지철; 및상기 소지철 상에 형성된 합금 도금층을 포함하고,상기 합금 도금층의 표면에서 깊이방향으로 15㎛까지, Ni 함량이 가장 높은 지점(Nimax)에서의 Ni 함량이 0.1~0.75 중량%인 내수소취성이 우수한 열간성형 부재.
- 청구항 7에 있어서,상기 합금 도금층은 Ni 농화층을 포함하고,상기 Ni 농화층은 글로 방전 분광법(Glow Discharge Optical Emission Spectrometry, GDS)을 이용하여, 상기 합금 도금층의 Ni 함량을 도출한 농도 프로파일 그래프에서, Ni의 함량이 가장 높은 지점(Nimax)에서 상기 부재의 표면방향으로 그래프의 기울기가 O이 되는 지점(Nio) 및 상기 Nimax에서 상기 부재의 깊이방향으로 상기 Nio와 동일한 함량을 갖는 지점(Nio') 사이의 폭인 내수소취성이 우수한 열간성형 부재.
- 청구항 8에 있어서,상기 Ni 농화층의 두께는 1~15㎛인 내수소취성이 우수한 열간성형 부재.
- 청구항 7에 있어서,상기 열간성형 부재의 확산성 수소량은 0.3 중량ppm 이하인 내수소취성이 우수한 열간성형 부재.
- 청구항 7에 있어서,상기 소지철의 주상은 마르텐사이트인 내수소취성이 우수한 열간성형 부재.
- 소지강판 및 상기 소지강판 표면에 형성된 Al계 도금층을 포함하고, 상기 Al계 도금층 내 Ni 평균 함량은 0.05~0.35 중량%인 블랭크를 제공하는 단계;상기 블랭크를 Ac3~975℃의 온도범위로 가열하는 단계; 및상기 가열된 블랭크를 프레스로 이송하여 성형하고, 20℃/s 이상의 냉각속도로 냉각하는 단계;를 포함하는 내수소취성이 우수한 열간성형 부재의 제조방법.
- 청구항 12에 있어서,상기 온도범위에서 1~1000초가 유지하는 내수소취성이 우수한 열간성형 부재의 제조방법.
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WO2019132293A1 (ko) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | 표면 외관이 우수한 열연용융아연도금강판 및 그 제조방법 |
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US6296805B1 (en) | 1998-07-09 | 2001-10-02 | Sollac | Coated hot- and cold-rolled steel sheet comprising a very high resistance after thermal treatment |
KR20160057418A (ko) * | 2013-09-13 | 2016-05-23 | 티센크루프 스틸 유럽 악티엔게젤샤프트 | 부식에 대한 보호를 제공하는 금속성 코팅이 제공된 강 부품의 제조 방법, 및 강 부품 |
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