Title of Invention: Aluminum-based alloy plated steel sheet with excellent workability and corrosion resistance and manufacturing method thereof
technical field
[One]
The present invention relates to an aluminum-based alloy plated steel sheet having excellent workability and corrosion resistance, and a method for manufacturing the same.
[2]
background
[3]
Conventionally, an aluminum (Al) plated steel sheet or a zinc (Zn) plated steel sheet has been used for hot forming, but there is a problem in that micro cracks occur or corrosion resistance deteriorates due to an alloy phase formed during heat treatment. In addition, aluminum (Al) plated steel sheet or zinc (Zn) plated steel sheet has a problem in that the plating layer is liquefied during hot forming and fused to the roll. In addition, in the case of an aluminum plated steel sheet, since there is no sacrificial corrosion resistance of aluminum, corrosion resistance after processing may become a problem.
[4]
In order to improve such corrosion resistance and hot formability, conventionally, an aluminum alloy plated steel sheet in which the plating layer is alloyed by controlling Si to 4% or less in the plating bath, and the alloying temperature is 700° C. and the alloying time is 20 seconds has been disclosed.
[5]
However, under the above conditions, since the alloying time is 20 seconds, it is difficult to perform an alloying treatment in a seal line, and there is a problem that strong cooling is required after alloying. In addition, as the Si content decreases, the plating bath temperature is very high, about 700° C., so there is a problem in that durability of structures such as sink rolls immersed in the plating bath is remarkably deteriorated.
[6]
In addition, when the plating layer is alloyed, it moves through many rolls when it finally reaches the pay-off reel.
[7]
(Patent Document 1) Korean Patent Publication No. 1997-0043250
[8]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[9]
According to one aspect of the present invention, it is an object of the present invention to provide an aluminum-based alloy-coated steel sheet having excellent adhesion properties and corrosion resistance during hot forming, and a method for manufacturing the same, while improving powdering properties generated when an aluminum plating layer is alloyed.
[10]
The object of the present invention is not limited to the above. Those of ordinary skill in the art to which the present invention pertains will have no difficulty in understanding the additional problems of the present invention from the contents throughout the present specification.
[11]
means of solving the problem
[12]
One aspect of the present invention is
[13]
holding grater;
[14]
an alloy plating layer formed on the base steel sheet; and
[15]
a non-alloyed plating layer formed on the alloyed plating layer;
[16]
The alloy plating layer contains, by weight, Fe: 35-50%, Zn: 1-20%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities,
[17]
The non-alloying plating layer contains, by weight, Zn: 1 to 30%, Si: 0.1 to 1.8%, the remainder Al and other unavoidable impurities,
[18]
It provides an aluminum-based alloy plated steel sheet having an interfacial roughness of 2.5 μm or less between the alloy plating layer and the base steel sheet.
[19]
[20]
In addition, another aspect of the present invention,
[21]
A method of manufacturing an aluminum-based alloy plated steel sheet used for hot press forming, comprising:
[22]
preparing a holding grater;
[23]
Obtaining an aluminum-plated steel sheet by immersing the base steel sheet in an aluminum plating bath containing, by weight, Zn: 3-30%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities;
[24]
After aluminum plating, a cooling step of supplying air heated to 200 ~ 300 ℃ to the aluminum plated steel sheet to form an oxide film on the surface of the aluminum plated steel sheet; and
[25]
Obtaining an aluminum-based alloy plated steel sheet through on-line alloying in which heat treatment is performed by continuously maintaining for 1 to 20 seconds in a heating temperature range of 550° C. or more and less than 650° C. after cooling; including, aluminum-based alloy plating A method for manufacturing a steel sheet is provided.
[26]
[27]
In addition, another aspect of the present invention provides a hot-formed member obtained by hot press forming the above-described aluminum-based alloy plated steel sheet.
[28]
Effects of the Invention
[29]
Advantageous Effects of Invention According to the present invention, it is possible to provide an aluminum-based alloy-coated steel sheet having excellent adhesion properties and corrosion resistance during hot forming, and a method for manufacturing the same, while improving powdering properties generated when the aluminum plating layer is alloyed.
[30]
Brief description of the drawing
[31]
1 is a photograph observed with a scanning electron microscope (SEM) of a cross-section of an aluminum-based alloy plated steel sheet prepared according to Inventive Example 1. FIG.
[32]
2 is a photograph observed with a scanning electron microscope (SEM) of a cross section of the aluminum-based alloy plated steel sheet prepared in Comparative Example 1. Referring to FIG.
[33]
3 is a photograph showing the results of evaluating the powdering properties for each Inventive Example 1 and Comparative Example 1.
[34]
Best mode for carrying out the invention
[35]
In the prior art, by adding a large amount of Si to the aluminum plating bath, a dense Fe-Al-Si alloy phase was formed in the plating layer, thereby suppressing diffusion of the base iron into the plating layer. This required a high alloying temperature and a long alloying time.
[36]
To improve this, on-line alloying was attempted by limiting the Si content to 0.5 to 4%, but as the Si content decreased, an Al-Fe alloy phase was quickly generated and the melting point of the plating layer increased. there was For this reason, since diffusion of Fe of the base iron into the plating layer is suppressed, there is a problem in that it is difficult to perform alloying on-line. In addition, when the plating layer is alloyed in this way, due to the brittle alloy phase, there is a problem in that powdering occurs due to the generation of stress due to the roll during assembly.
[37]
In order to solve this problem, as a result of intensive study, the composition of the plating layer was composed of two layers: an alloy phase (alloyed plating layer) that was partially alloyed and a non-alloyed phase that was not alloyed (non-alloyed plating layer; Al-based plating layer). At the same time, by controlling the interfacial roughness between the alloy plating layer and the base steel sheet in a specific range, the problems of the prior art described above are solved, powdering does not occur during on-line operation, and stable production can be performed. In addition, it was discovered that heat resistance and corrosion resistance can be improved due to the alloy phase formed on the plating layer, and the present invention was completed.
[38]
Therefore, according to the present invention, alloying of the plating layer is possible in a relatively short time of 20 seconds or less, and at the same time, it is not only excellent in cauterization, corrosion resistance and adhesion of the plating layer, but also effectively provides an aluminum-based alloy plated steel sheet with improved powdering properties can do.
[39]
Hereinafter, the present invention will be described in detail. First, an aluminum-based alloy plated steel sheet, which is an aspect of the present invention, will be described in detail.
[40]
[Aluminum-based alloy plated steel sheet]
[41]
That is, one aspect of the present invention is
[42]
holding grater;
[43]
an alloy plating layer formed on the base steel sheet; and
[44]
a non-alloyed plating layer formed on the alloyed plating layer;
[45]
The alloy plating layer contains, by weight, Fe: 35-50%, Zn: 1-20%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities,
[46]
The non-alloying plating layer contains, by weight, Zn: 1 to 30%, Si: 0.1 to 1.8%, the remainder Al and other unavoidable impurities,
[47]
It provides an aluminum-based alloy plated steel sheet having an interfacial roughness of 2.5 μm or less between the alloy plating layer and the base steel sheet.
[48]
That is, the aluminum-based alloy plated steel sheet according to an aspect of the present invention may include a base steel sheet and an alloy plating layer formed on the base steel sheet, and the alloy plating layer may be formed on one or both surfaces of the base steel sheet. In addition, according to an aspect of the present invention, the non-alloying plating layer may be formed on the alloying plating layer. Accordingly, the aluminum-based alloy plated steel sheet may be provided with the non-alloyed plating layer on at least one surface of the base steel sheet, and the alloyed plating layer may be provided between the base steel sheet and the non-alloyed plating layer.
[49]
Hereinafter, the alloy plating layer and the non-alloy plating layer will be separately described, and first, the alloy plating layer will be described.
[50]
According to one aspect of the present invention, the alloy plating layer has a composition including, by weight, Fe: 35-50%, Zn: 1-20%, Si: 0.1-1.5%, the balance Al and other unavoidable impurities, the ratio The alloy plating layer has a composition including, by weight, Zn: 1 to 30%, Si: 0.1 to 1.5%, the remainder Al and other unavoidable impurities.
[51]
According to one aspect of the present invention, in the alloy plating layer, Zn plays an important role in improving the adhesion and corrosion resistance of the plated steel sheet as well as improving the adhesion of the alloy plating layer after the alloying treatment. Therefore, according to one aspect of the present invention, it is preferable that the Zn content in the alloy plating layer is 1 to 20%, and if the Zn content in the alloy plating layer is less than 1%, the effect of corrosion resistance cannot be expected, and in the alloy plating layer When the Zn content exceeds 20%, there is a problem in that the sintering property is deteriorated.
[52]
In addition, according to an aspect of the present invention, the Si content in the alloy plating layer is preferably 0.1 to 1.5%, and if the Si content in the alloy plating layer is less than 0.1%, the interfacial roughness between the alloy plating layer and the base steel sheet is too large If a problem occurs in the plating layer in terms of securing adhesion, and the Si content in the alloying plating layer exceeds 1.5%, Si is dissolved in the Fe-Al alloy phase to suppress the diffusion of Fe diffused in the base iron and thus alloying It is undesirable as the temperature may increase.
[53]
In addition, according to one aspect of the present invention, the alloy plating layer may optionally further include Mn, which is plated by immersing the steel sheet in an aluminum plating bath, and then Mn, which is a component included in the steel sheet through alloying heat treatment. This is because it flows into the plating layer side. As a result of this diffusion, Mn of 2% or less may be further included in the alloy plating layer of the aluminum-based alloy-coated steel sheet. The upper limit of the Mn content is preferably 2% or less in order to secure plating adhesion. Mn is an Al-Fe alloy phase type As an element substituting Fe in the castle, it plays a role in improving the adhesion with the base iron, but when it is 2% or more, the alloy phase of Al-Fe is formed into a dense Al-Fe (Mn) phase, and alloying may be delayed. In addition, since the Mn content in the alloy plating layer includes a case of 0%, the lower limit thereof is not specifically limited.
[54]
In addition, according to one aspect of the present invention, as components such as Fe contained in the base steel sheet are diffused through the above-described alloying treatment, in the alloy plating layer, the content of Fe is preferably 35-50%. By satisfying the above-mentioned composition, it is possible to secure the desired seizure properties and corrosion resistance in the present invention, and it is also possible to secure the powdering resistance.
[55]
In addition, according to one aspect of the present invention, in the alloy plating layer, the Al content is preferably 30 to 65% for achieving the object of the present invention, more preferably 31.4 to 63.5%. By setting the Al content in the alloy plating layer to 30% or more, the Fe-Al alloy phase having a high melting point is formed, thereby having the effect of suppressing the occurrence of sintering properties and micro-cracks. However, when the Al content in the alloy plating layer exceeds 65%, the melting point is lowered due to the formation of an Al-base alloy phase, so there is a problem in that the sinterability during heat treatment is inferior.
[56]
In addition, according to one aspect of the present invention, the thickness of the alloy plating layer may be 5 ~ 25㎛. Corrosion resistance can be ensured by the thickness of the said alloy plating layer being 5 micrometers or more, and weldability can be ensured by setting it as 25 micrometers or less. Therefore, in this invention, it is preferable that it is 5-25 micrometers, and, as for the thickness of an alloy plating layer, it is more preferable that it is 10-25 micrometers.
[57]
On the other hand, according to one aspect of the present invention, in the alloy plating layer, components such as Fe (or Mn) contained in the base steel sheet are diffused into the aluminum plating layer by alloying heat treatment after plating, and as a result, intermetallic compounds of Fe and Al An alloy plating layer mainly composed of may be formed. The alloy plating layer may be mainly composed of an alloy phase of an Fe-Al-based intermetallic compound, and elements such as Zn, Mn, and Si may be dissolved in the alloy plating layer. Specifically, the alloy plating layer contains at least 80% of the Fe-Al-based intermetallic compound such as FeAl 3 and Fe 2Al 5 (that is, the alloy plating layer includes at least one selected from the group consisting of FeAl 3 and Fe 2Al 5 and The alloy phase may include 80% or more as a phase fraction, which can be confirmed by phase analysis using XRD (X-Ray Diffraction) for an aluminum-based alloy plated steel sheet), more preferably 90% may include more than one. In addition, according to one aspect of the present invention, the alloy plating layer may be formed of an alloy phase in which Zn, Mn, and/or Si are solid-dissolved based on the aforementioned alloy phase of the Fe-Al-based intermetallic compound.
[58]
In addition, according to one aspect of the present invention, the interfacial roughness of the alloy plating layer and the base steel sheet may be 2.5㎛ or less, more preferably in the range of 0.03 ~ 2.5㎛. Thereby, good adhesion of the plating layer can be ensured. On the other hand, in the present specification, the interfacial roughness (Ra) is an average value obtained by arithmetically calculating the degree of deviation from the profile center line up and down as shown in Equation 1 below with respect to the interface formed between the alloy plating layer and the base steel sheet. means Therefore, mathematically, it corresponds to the height (amplitude) of the rectangular area having an area equal to the sum of the areas of all peaks and valleys of the roughness curve. At this time, the interfacial roughness (Ra) is taken with a scanning transfer microscope (SEM) of a cross section in the thickness direction (meaning a direction perpendicular to the rolling direction) of the aluminum-based alloy plated steel sheet, the alloy plating layer and the base steel sheet It can be measured by observing the interface.
[59]
[Equation 1]
[60]

[61]
(In Equation 1, Ra represents the interfacial roughness of the above-mentioned alloy plating layer and the base steel sheet, l represents the total length of the interface line to be measured, Z(x) is the position change of the interface line along the x-axis longitudinal direction is a function representing
[62]
On the other hand, although not particularly limited, according to one aspect of the present invention, the interfacial roughness (Ra') for the interface between the alloyed plating layer and the non-alloyed plating layer may also be measured in the same manner as in the above-described method, and the alloy plating layer The interfacial roughness (Ra') of the non-alloyed plating layer may be greater than the interfacial roughness (Ra) between the alloyed plating layer and the base steel sheet. Specifically, Ra' may be in the range of 1.02 to 2 times that of Ra. Through this, the adhesion of the plating layer can be further improved.
[63]
On the other hand, according to one aspect of the present invention, a non-alloying plating layer is formed on the alloying plating layer, and the non-alloying plating layer is Zn: 1 to 30%, Si: 0.1 to 1.8%, remainder Al and other unavoidable impurities by weight%. include As such, by forming the non-alloying plating layer on the alloying plating layer, a relatively soft plating layer is formed on the surface, and thus powdering due to the stress caused by the roll during operation due to the brittle alloy phase is prevented. can be suppressed
[64]
In addition, according to one aspect of the present invention, the Zn content in the non-alloying plating layer may be greater than the Zn content in the alloying plating layer, or the Si content in the non-alloying plating layer may be greater than or equal to the Si content in the alloying plating layer. Alternatively, the Al content in the non-alloyed plating layer may be greater than the Al content in the alloyed plating layer. By satisfying the composition described above, powdering properties can be improved.
[65]
Further, according to an aspect of the present invention, the Zn content in the non-alloyed plating layer may be 1.5 to 30%, or the Al content in the non-alloyed plating layer may be 65 to 98.9%.
[66]
In addition, according to one aspect of the present invention, the thickness of the non-alloying plating layer is preferably 0.5-15 μm, more preferably 1-12 μm, and the thickness of the non-alloying plating layer may be smaller than or equal to the thickness of the alloy plating layer. have.
[67]
In addition, according to one aspect of the present invention, the thickness of the alloy plating layer may be 50% or more of the total thickness of the alloy plating layer and the non-alloy plating layer, more preferably in the range of 50 to 95%. By satisfying this, it is possible to provide a plated steel sheet for hot press forming with improved caustic properties, corrosion resistance, powdering properties, and productivity.
[68]
According to one aspect of the present invention, the fraction of the alloy phase of the Fe-Al-based intermetallic compound in the entire plating layer is preferably 50% or more, and more preferably 70% or more.
[69]
By satisfying the fraction of the alloy phase described above, it is possible to improve the sintering property, corrosion resistance, and powdering property. According to an aspect of the present invention, the thickness of the non-alloyed plating layer may be smaller than the thickness of the alloyed plating layer, thereby improving powdering properties.
[70]
In addition, according to one aspect of the present invention, the base steel sheet included in the above-mentioned plated steel sheet is a steel sheet for hot press forming, and is not particularly limited if used for hot press forming. However, to give one non-limiting example, a steel sheet containing Mn in the range of 1 to 10% may be used as the steel sheet. Or, more preferably, as a base steel sheet, by weight%, C: 0.05 to 0.3%, Si: 0.1 to 1.5%, Mn: 0.5 to 8%, B: 50 ppm or less, the balance Fe and other unavoidable impurities. Branches can use a steel plate.
[71]
That is, according to the present invention, it is possible to provide an aluminum-based alloy plated steel sheet having excellent corrosion resistance and adhesion of the plating layer while suppressing the seizure of the plating layer attached to the press die or roll generated during hot forming.
[72]
[73]
[Manufacturing method of aluminum alloy plated steel sheet]
[74]
Hereinafter, an example of a method for manufacturing an aluminum-based alloy plated steel sheet used for hot press forming according to an aspect of the present invention will be described. However, the following manufacturing method of the aluminum-based alloy plated steel sheet for hot press forming is an example, and the aluminum-based alloy plated steel sheet for hot press forming of the present invention does not necessarily have to be manufactured by the present manufacturing method.
[75]
Specifically, another aspect of the present invention is
[76]
A method for manufacturing an aluminum-based alloy plated steel sheet used for hot press forming, comprising:
[77]
preparing a holding grater;
[78]
Obtaining an aluminum-plated steel sheet by immersing the base steel sheet in an aluminum plating bath containing, by weight, Zn: 3-30%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities;
[79]
After aluminum plating, a cooling step of supplying air heated to 200 ~ 300 ℃ to the aluminum plated steel sheet to form an oxide film on the surface of the aluminum plated steel sheet; and
[80]
Obtaining an aluminum-based alloy plated steel sheet through on-line alloying in which heat treatment is performed by continuously maintaining for 1 to 20 seconds in a heating temperature range of 550° C. or more and less than 650° C. after cooling; including, aluminum-based alloy plating A method for manufacturing a steel sheet is provided.
[81]
First, a base steel sheet is prepared in order to manufacture an aluminum alloy plated steel sheet. For the base steel sheet, the above-described description may be applied in the same manner.
[82]
Then, before performing the following plating, the base steel sheet may be heat-treated at 650 to 850° C., but the present invention is not particularly limited thereto. The heat treatment is performed at a temperature above recrystallization to prevent work hardening of the material in the continuous plating process and to maintain the base steel sheet at a higher temperature than the plating bath to improve plating properties. When the heat treatment temperature is less than 650° C., deformation and meandering of the material may occur due to work hardening when passing through a roll such as a continuous process. Alternatively, when the heat treatment temperature exceeds 850° C., Mn and Si present in the base steel sheet may be concentrated on the surface of the base steel sheet to form an oxide, thereby deteriorating the plating property. Therefore, before plating, the heat treatment temperature of the base steel sheet can be controlled to 650 ~ 850 ℃, more preferably, before the plating, the lower limit of the heat treatment temperature of the base steel sheet can be 680 ℃, Before plating, the upper limit of the heat treatment temperature of the base steel sheet may be 830 ℃.
[83]
Next, the aluminum-based plated steel sheet according to an aspect of the present invention, Zn: 3 to 30%, Si: 0.1 to 1.5%, the remainder Al and other unavoidable impurities in weight % on the surface of the base steel sheet. It can be obtained by performing hot-dip aluminum plating using a bath, cooling continuously in the plating process, and then performing an on-line alloying treatment in which heat treatment is performed immediately.
[84]
Specifically, plating is performed by immersing the base steel sheet in a hot-dip aluminum plating bath, and the composition of the plating bath may include Zn: 3 to 30%, Si: 0.1 to 1.5%, the remainder Al and other unavoidable impurities, and more Preferably, Zn: 5 to 30%, Si: 0.1 to 1.5%, the balance may include Al and other unavoidable impurities. Alternatively, according to an aspect of the present invention, the hot-dip aluminum plating bath may include Zn: 5 to 30%, Si: 0.1 to 0.5%, the remainder Al and other unavoidable impurities.
[85]
According to an aspect of the present invention, Zn added to the aluminum plating bath is preferably added in an amount of 3 to 30% by weight. When the Zn content exceeds 30%, since a large amount of ash in the plating bath is generated, there is a problem in that workability is deteriorated due to generation of dust and the like. In addition, if the Zn content is less than 3%, the melting point of the plating bath is not significantly reduced, and Zn does not remain in the plating layer due to evaporation of Zn during alloying, so it is difficult to expect the effect of improving corrosion resistance. However, in order to further maximize the effect of the present invention, the lower limit of the Zn content is preferably 5%, and the upper limit of the Zn content is more preferably 20%.
[86]
In addition, according to one aspect of the present invention, the amount of Si added to the aluminum plating bath is preferably 0.1 to 1.5% by weight. If the Si content in the aluminum plating bath is less than 0.1%, the interfacial roughness between the alloy plating layer and the base steel sheet is too large to obtain the effect of improving plating adhesion, and when the Si content in the aluminum plating bath exceeds 1.5%, Fe-Al There is a problem in that the alloying temperature is increased because Si is dissolved in the alloy phase to suppress the diffusion of Fe diffused in the base iron.
[87]
On the other hand, according to one aspect of the present invention, it is preferable to manage the temperature of the plating bath as high as 20 to 50°C compared to the melting point (Tb) of the plating bath (that is, Tb+20°C or more and Tb+50°C or less). . By controlling the temperature of the plating bath to Tb+20°C or higher, it is possible to control the plating adhesion amount due to the fluidity of the plating bath, and by controlling the temperature of the plating bath to Tb+50°C or lower, structural erosion in the plating bath is prevented. can be prevented
[88]
In addition, according to one aspect of the present invention, during the plating, the plating amount per side (the amount of adhesion per side of the plating layer) may be 20 to 100 g/m 2 , which after immersing the steel sheet in the hot-dip aluminum plating bath, air It can be controlled by applying an air wipping process. When the plating amount per side during the plating is 20 g/m 2 or more, the corrosion resistance effect is exhibited, and when the plating amount per single side during the plating is 100 g/m 2 or less, there is an effect that the plating layer can be alloyed as a whole.
[89]
Subsequently, after aluminum plating, air heated to 200 to 300° C. may be supplied to the aluminum-plated steel sheet to be cooled to form an oxide film on the surface of the aluminum-plated steel sheet. This cooling step is important in the present invention in that it is a means of forming a uniform alloy layer. That is, by supplying and exposing air heated to 200 to 300 ° C. to the aluminum plated steel sheet during cooling, an oxide film (aluminum oxide film; AlO x ) is formed on the surface of the aluminum plated steel sheet.
[90]
According to one aspect of the present invention, as described above, before the alloying treatment, an oxide film can be formed on the surface of the aluminum-plated steel sheet by 10% or more (more preferably 10% or more and 20% or less) with respect to the total thickness of the hot-dip aluminum plating layer. have. As described above, by forming 10% or more of the oxide film, it is possible to prevent Zn contained in the plating layer from volatilizing during the alloying process, and thus it is possible to secure excellent sintering property, corrosion resistance and adhesion of the plating layer.
[91]
Next, an on-line alloying treatment in which heat treatment is continuously performed immediately after the above-described cooling may be performed. Through this alloying heat treatment, Fe and/or Mn of the base steel sheet may be diffused into the aluminum plating layer to form an alloy plating layer.
[92]
Specifically, in the present invention, the alloying treatment temperature is 550 °C or more and less than 650 °C, and the holding time may be 1 to 20 seconds. In the present invention, the on-line alloying process refers to a process of heat treatment by increasing the temperature after hot-dip aluminum plating. In the online alloying heat treatment method according to the present invention, since the heat treatment for alloying starts before the plating layer is cooled and hardened after hot-dip aluminum plating, alloying is possible in a short time. In the conventionally known plating layer composition system of aluminum-coated steel sheet, since the alloying rate was slow and sufficient alloying could not be completed within a short time, it was difficult to apply an on-line alloying method in which heat treatment was performed immediately after plating. However, in the present invention, alloying of the aluminum plating layer can be achieved despite a relatively short heat treatment time of 1 to 20 seconds by controlling the composition and manufacturing conditions of the plating bath that affect the alloying rate.
[93]
According to one aspect of the present invention, the alloying heat treatment temperature may be in the range of 550 °C or more and less than 650 °C. The alloying heat treatment temperature is based on the surface temperature of the steel sheet to be heat treated, and if the alloying heat treatment temperature is less than 550° C., there is a problem in that the alloy phase of the plating layer is formed in 50% or less, and if the alloying heat treatment temperature is 650° C. or more, the plating layer There is a problem in that powdering properties may occur due to complete alloying.
[94]
In addition, according to one aspect of the present invention, the holding time during the alloying heat treatment may be performed in the range of 1 to 20 seconds. In the present invention, the holding time during the alloying heat treatment means the time during which the heating temperature (including deviation ±10° C.) is maintained in the steel sheet. By making the said holding time into 1 second or more, sufficient alloying becomes possible, and there exists an effect of ensuring productivity by making the said holding time into 20 seconds or less.
[95]
In addition, according to one aspect of the present invention, in the plated steel sheet manufactured through the present invention, the Fe content in the alloying plated layer can be expressed by the following relational formula 1, and the Zn, Si content in the heat treatment temperature during alloying and the plating bath By controlling in an appropriate range, the effect of excellent sintering property, corrosion resistance, and/or plating layer adhesiveness can be exhibited easily.
[96]
[Relational Expression 1]
[97]
160 - 0.41×[T]+3.35×10 -4×[T 2] - 0.3×[wt%Zn]- 3×[wt%Si] ≤ [wt%Fe] ≤ 180 - 0.41×[T]+3.35 ×10 -4×[T 2] - 0.3×[wt%Zn]- 3×[wt%Si]
[98]
[In relation 1, [T] represents the alloying heat treatment temperature (°C), [wt%Zn] represents the Zn wt% content in the plating bath, and [wt%Si] represents the Si wt% content in the plating bath , and [wt%Fe] represents the content of Fe by weight in the alloy plating layer.]
[99]
According to one aspect of the present invention, in order to further improve the effect of the present invention, the lower limit of the holding time during the alloying heat treatment may be 2 seconds, more preferably 5 seconds. Similarly, the upper limit of the holding time during the alloying heat treatment may be 15 seconds, more preferably 10 seconds.
[100]
As described above, in the prior art, since diffusion of Fe is suppressed by the inclusion of Si, it was impossible to alloy in a short time of 20 seconds or less, whereas, according to the present invention, the composition of the plating bath and conditions during the alloying heat treatment are controlled. By doing so, alloying can be made in a relatively short time of 20 seconds or less.
[101]
On the other hand, the method of manufacturing an aluminum alloy plated steel sheet according to an aspect of the present invention may further include the step of cooling after the alloying treatment.
[102]
According to an aspect of the present invention, the cooling may be performed at an average cooling rate of 5 to 50° C./s to 300° C. or less based on the surface temperature of the steel sheet. Meanwhile, the cooling may be air cooling or mist cooling, and according to one aspect of the present invention, most preferably, the cooling may be mist cooling.
[103]
On the other hand, according to one aspect of the present invention, more preferably by setting the average cooling rate to 10 ~ 30 ℃ / s, there is an effect that can be cooled on-line using the existing hot-dip plating line without additional equipment. In addition, according to one aspect of the present invention, the cooling can be carried out for 5 to 20 seconds, and by setting the cooling time to 10 seconds or more, a sufficient cooling effect can be exhibited.
[104]
On the other hand, another aspect of the present invention provides a hot formed member obtained by hot press forming the above-described aluminum alloy plated steel sheet.
[105]
The hot press forming may use a method generally used in the art. For example, after the plated steel sheet is heated in a temperature range of 800 to 950° C. for 3 to 10 minutes, the heated steel sheet may be hot formed into a desired shape using a press, but is not limited thereto.
[106]
In addition, the composition of the holding steel sheet of the hot press-formed member may be the same as the composition of the holding steel sheet described above.
[107]
Modes for carrying out the invention
[108]
Hereinafter, the present invention will be described in more detail through examples. However, it is necessary to note that the following examples are only for exemplifying the present invention and not limiting the scope of the present invention. This is because the scope of the present invention is determined by the matters described in the claims and matters reasonably inferred therefrom.
[109]
(Example)
[110]
First, having the composition shown in Table 1 below as a steel sheet After preparing a cold-rolled steel sheet for hot press forming with a thickness of 1.2 mm, the base steel sheet was immersed and ultrasonically cleaned to remove materials such as rolling oil present on the surface.
[111]
[Table 1]
Element C Si Mn Ti B Fe
Content (%) 0.22% 0.25% Mn:1.3% 0.03% 25ppm bal
[112]
Thereafter, after heat treatment at an annealing temperature of 800° C. and an annealing time of 50 seconds in a furnace maintained in a reducing atmosphere, the base steel sheet is Zn: 3 to 30%, Si: 0.1 to 1.5%, the balance of the composition of Al It was immersed in the plating bath which satisfies, and aluminum plating was performed. When the plating bath was immersed, the immersion temperature was maintained at the same temperature as that of the plating bath, and the plating bath was maintained at a temperature that was raised by 40° C. for the melting point (Tb) of each plating component system. The plating amount was kept constant at 60 g/m 2 on one side using air wiping to compare alloying.
[113]
[Table 2]
Category Plating bath composition [wt%] Alloying temperature
[℃] alloying time
[candle]
AlZnSi
Comparative Example 1 bal - - 720 15
Comparative Example 2 bal 1.5 7.7 680 20
Comparative Example 3 bal - 2 700 15
Comparative Example 4 bal 3 5.5 670 20
Comparative Example 5 bal - 2 680 15
Comparative Example 6 bal 18 8.8 650 20
Comparative Example 7 bal - 2 680 10
Comparative Example 8 bal 30 8.8 670 20
Comparative Example 9 bal 37.5 9.9 680 15
Comparative Example 10 bal - 1.1 700 10
Invention example 1 bal 1.5 0.1 620 5
Invention example 2 bal 1.5 1.7 640 10
Invention example 3 bal 7.5 0.11 630 5
Invention example 4 bal 7.5 1.65 630 10
Invention example 5 bal 22.5 0.1 600 5
Invention example 6 bal 22.5 1.1 580 5
Invention example 7 bal 22.5 1.7 630 5
Invention example 8 bal 30 0.1 590 10
Invention example 9 bal 30 1.1 610 7
Invention example 10 bal 30 1.7 640 5
[114]
Then, the aluminum-plated steel sheet was cooled by supplying air heated to 200 to 300° C. to the aluminum-plated steel sheet, and during cooling, an oxide film of 10% based on the total thickness of the hot-dip aluminum plating layer was controlled to be formed. Thereafter, the alloying heat treatment was performed to prepare an aluminum-based alloy plated steel sheet shown in Table 2 below. On the other hand, among the experimental examples in Table 3 below, the alloying was carried out in the range of 650 ~ 750 ℃ ​​in the example indicated as full alloying, the example indicated as partial alloying was alloyed in the range of 550 ℃ or more and less than 650 ℃. Thereafter, the aluminum alloy plated steel sheet was manufactured by cooling with air cooling to 300° C. or less based on the surface temperature of the steel sheet.
[115]
[Table 3]
Classification Alloyed plated layer Non-alloyed plated layer Ra* Whether fully alloyed or partially alloyed
[Full/Partial] T*
component alloy layer
thickness
[㎛] component non-alloy layer
thickness
[μm]
Al Zn Mn Fe Si Al Zn Si
Comparative Example 1 bal 1 0 46 0 10 bal - - - 0.8 Complete 100%
Comparative Example 2 bal 1 2 50 7 30 bal 1.5 8.4 5 3.0 Part 86%
Comparative Example 3 bal 2 1 44 2 20 bal - - - 1.2 Complete 100%
Comparative Example 4 bal 2 1 45 5 30 bal 3 6 5 1.2 Part 86%
Comparative Example 5 bal 10 3 47 2 20 bal - - - 3.2 Complete 100%
Comparative Example 6 bal 12 2 39 8 5 bal 18 9.6 20 3.2 Part 20%
Comparative Example 7 bal 15 1 38 2 5 bal - - - 0.6 Complete 100%
Comparative Example 8 bal 20 2 35 8 10 bal 30 9.6 20 0.6 Part 33%
Comparative Example 9 bal 25 3 36 9 10 bal 37.5 10.8 15 1.2 Part 40%
Comparative Example 10 bal 35 5 40 1 25 bal - 1.2 - 0.4 Complete 100%
Invention Example 1 bal 1 0.5 35 0.1 10 bal 1.5 0.1 10 1.2 Part 50%
Invention Example 2 bal 1 0.3 50 1.5 20 bal 1.5 1.8 5 2.5 Part 80%
Inventive Example 3 bal 5 1 37 0.1 10 bal 7.5 0.12 5 2.0 Part 67%
Invention Example 4 bal 5 0.5 48 1.5 20 bal 7.5 1.8 1 2.0 Part 95%
Inventive Example 5 bal 15 0.5 46 0.1 15 bal 22.5 0.1 1 0.8 Part 94%
Example 6 bal 15 0.1 42 1 15 bal 22.5 1.2 5 0.8 Part 75%
Inventive Example 7 bal 15 0.7 35 1.5 20 bal 22.5 1.8 6 0.4 Part 77%
Invention Example 8 bal 20 1.5 47 0.1 12 bal 30 0.1 12 1.0 Part 50%
Invention example 9 bal 20 1 43 1 15 bal 30 1.2 10 1.0 Part 60%
Example 10 bal 20 2 36 1.5 25 bal 30 1.8 5 1.0 Part 83%
[116]
Ra*: Interfacial roughness between the alloy plating layer and the base steel sheet [㎛]
[117]
T*: thickness fraction of the alloy layer compared to the thickness of the entire plating layer (alloyed plating layer and non-alloyed plating layer) [%]
[118]
In the aluminum alloy plated steel sheet manufactured by the above method, the content and thickness of each component in the alloy plating layer were measured and shown in Table 3, and the components in the alloy plating layer were wet using ICP (Inductive Coupled Plasma Spectroscopy). method, and the thickness was measured by observing the cross section with an electron microscope.
[119]
On the other hand, for the evaluation of the characteristics of the aluminum-based alloy plated steel sheet, the corrosion resistance, corrosion resistance, powdering property and productivity were evaluated in the following manner, and the evaluation results are shown in Table 4 below.
[120]
[Adhesiveness]
[121]
The plated steel sheet thus prepared was heated at 900° C. for 5 minutes to evaluate the physical properties of the plating, and then visually observed whether the alloy plating layer was fused to the die and evaluated according to the following criteria.
[122]
○: No burning
[123]
×: Die adsorption due to melting of the plating layer occurs
[124]
[Corrosion resistance]
[125]
After the salt spray test for 720 hours, the corrosion product formed on the surface was removed, and the depth of corrosion formed by corrosion was measured.
[126]
○: 70㎛ or less
[127]
×: more than 70 μm
[128]
[Powdering properties]
[129]
The peeling of the plating layer was evaluated using a 60° bending experiment, and is shown in Table 3 below.
[130]
[productivity]
[131]
Productivity was evaluated based on the following criteria by measuring the time required for alloying.
[132]
○: less than 15 seconds
[133]
△: 15 seconds or more and 20 seconds or less
[134]
×: more than 20 seconds
[135]
[Table 4]
Firing property Corrosion resistance Powdering property Productivity
Comparative Example 1 ○ ○ × △
Comparative Example 2 ○ ○ × △
Comparative Example 3 ○ ○ × △
Comparative Example 4 ○ ○ × △
Comparative Example 5 ○ ○ × △
Comparative Example 6 × × ○ △
Comparative Example 7 ○ × × ○
Comparative Example 8 × ○ ○ △
Comparative Example 9 × ○ ○ △
Comparative Example 10 ○ ○ × ○
Invention Example 1 ○ ○ ○ ○
Invention Example 2 ○ ○ ○ ○
Invention Example 3 ○ ○ ○ ○
Invention Example 4 ○ ○ ○ ○
Invention Example 5 ○ ○ ○ ○
Invention Example 6 ○ ○ ○ ○
Invention Example 7 ○ ○ ○ ○
Invention Example 8 ○ ○ ○ ○
Invention Example 9 ○ ○ ○ ○
Invention Example 10 ○ ○ ○ ○
[136]
As shown in Table 4, Inventive Examples 1 to 10, which satisfy the composition of the alloyed plated layer, the composition of the non-alloyed plated layer, and the manufacturing conditions specified in the present invention, have excellent effects of improving the sintering property, corrosion resistance, powdering property and productivity. did.
[137]
On the other hand, Comparative Examples 1 to 10, which do not satisfy any one of the composition of the alloyed plated layer, the composition of the non-alloyed plated layer, and the manufacturing conditions specified in the present invention, have poor cauterization, corrosion resistance, powdering properties, and productivity. did.
[138]
In particular, a photograph observed with a scanning electron microscope (SEM) of the cross section of the aluminum-based alloy plated steel sheet obtained from Invention Example 1 is shown in FIG. 1 , and it is confirmed that the interfacial roughness between the alloy plating layer and the base steel sheet measured therefrom is 2.5 μm or less did. In addition, by applying the same method as the measuring method of Ra, the interfacial roughness (Ra') of the alloyed plated layer and the non-alloyed plated layer was measured, and the Ra' value is in the range of 1.02 to 2 times compared to the Ra value. It was confirmed that it was larger than the interfacial roughness (Ra) between the plating layer and the base steel sheet.
[139]
In addition, with respect to the aluminum-based alloy plated steel sheet obtained from Invention Example 1, by phase analysis using X-Ray Diffraction (XRD), the alloy plating layer formed on the base steel sheet is Fe 2Al 5 and FeAl 3 selected from the group consisting of 1 It was confirmed that more than 80% of the alloy phase was included in the phase fraction.
[140]
On the other hand, a photograph of a cross-section of the aluminum-based alloy plated steel sheet obtained from Comparative Example 1 observed with a scanning electron microscope is shown in FIG. 2 , and the interfacial roughness between the alloyed plated layer and the base steel sheet measured therefrom exceeded 2.5 μm. The results of evaluating the powdering properties of Inventive Example 1 and Comparative Example 1 are shown in FIG. 3 , and FIG. 3 (a) shows Inventive Example 1 and FIG. 3 (b) shows Comparative Example 1. The experimental results Through the comparison, in the case of Inventive Example 1, it was confirmed that the powdering property was more improved compared to Comparative Example 1.
Claims
[Claim 1]
holding grater; an alloy plating layer formed on the base steel sheet; and a non-alloying plating layer formed on the alloying plating layer, wherein the alloying plating layer is Fe: 35-50%, Zn: 1-20%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities by weight% Including, wherein the non-alloyed plating layer is, by weight %, Zn: 1 to 30%, Si: 0.1 to 1.8%, the balance includes Al and other unavoidable impurities, the interfacial roughness of the alloy plating layer and the base steel sheet is 2.5㎛ or less, Aluminum alloy plated steel sheet.
[Claim 2]
According to claim 1, wherein the thickness of the alloy plating layer is 5 ~ 25㎛, the non-alloying plating layer The thickness is 1 to 12㎛, aluminum-based alloy plated steel sheet.
[Claim 3]
The aluminum-based alloy-coated steel sheet according to claim 1, wherein the Zn content in the non-alloyed plated layer is greater than the Zn content in the alloyed plated layer.
[Claim 4]
The aluminum-based alloy-coated steel sheet according to claim 1, wherein the thickness of the alloy plating layer is 50% or more of the total thickness of the alloy plating layer and the non-alloy plating layer.
[Claim 5]
According to claim 1, wherein the base steel sheet by weight, by weight%, C: 0.05 to 0.3%, Si: 0.1 to 1.5%, Mn: 0.5 to 8%, B: 50ppm or less, the balance Fe and other unavoidable impurities Containing, aluminum-based alloy plated steel sheet.
[Claim 6]
The aluminum-based alloy-coated steel sheet according to claim 1, wherein the Si content in the alloy plating layer is 0.1 to 0.5% by weight.
[Claim 7]
A method of manufacturing an aluminum-based alloy plated steel sheet used for hot press forming, the method comprising: preparing a base steel sheet; Obtaining an aluminum-plated steel sheet by immersing the base steel sheet in an aluminum plating bath containing, by weight, Zn: 3-30%, Si: 0.1-1.5%, the remainder Al and other unavoidable impurities; After aluminum plating, a cooling step of supplying air heated to 200 ~ 300 ℃ to the aluminum plated steel sheet to form an oxide film on the surface of the aluminum plated steel sheet; and obtaining an aluminum-based alloy plated steel sheet through on-line alloying in which heat treatment is performed by continuously maintaining for 1 to 20 seconds in a heating temperature range of 550° C. or more and less than 650° C. after cooling. A method for manufacturing a plated steel sheet.
[Claim 8]
The method of claim 7, further comprising cooling after the alloying treatment.
[Claim 9]
The method of claim 7, wherein, during the plating, the plating amount per side is 20-100 g/m 2 .
[Claim 10]
The method of claim 8, wherein the cooling after the alloying treatment is air cooling.
[Claim 11]
The method according to claim 7, wherein the oxide film is formed on the surface by 10% or more of the total thickness of the hot-dip aluminum plating layer.
[Claim 12]
A hot-formed member obtained by hot press forming the aluminum-based alloy-plated steel sheet according to claim 1 .