JP2016029214A - Steel plate for hot press and method for producing hot press member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a steel plate for hot press with excellent oxidation resistance capable of preventing the generation of scale and ZnO at the time of hot press, and a method for producing a hot press member using the same.SOLUTION: A steel plate for hot press has, on the surface of a steel plate, a plating layer that comprises 10-25 mass% Ni with the balance being Zn and inevitable impurities and has its coating weight of 10-90 g/m, the η phase content of the plating layer is 5 mass% or less, and a base steel plate of the plating layer has a chemical composition comprising, by mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P: 0.01-0.1%, S: 0.05% or less, Al: 0.1% or less, and N: 0.01% or less with the balance being Fe and inevitable impurities.SELECTED DRAWING: None

Description

  The present invention relates to a steel sheet for hot pressing suitable for manufacturing an automobile underbody member, a vehicle body structural member, and the like by hot pressing, and a method for manufacturing a hot pressing member using the same.

  2. Description of the Related Art Conventionally, many undercarriage members and body structure members of automobiles are manufactured by pressing a steel plate having a predetermined strength. In recent years, from the viewpoint of the preservation of the global environment, there has been a strong desire to reduce the weight of automobile bodies, and efforts have been made to increase the strength of steel sheets to be used and to reduce their thickness. However, as the strength of the steel plate increases, the press workability decreases, and it is often difficult to process the steel plate into a desired member shape.

  Therefore, Patent Document 1 describes a process called a hot press that enables both easy processing and high strength by simultaneously processing a heated steel sheet using a die and punch die and simultaneously cooling it. Technology has been proposed. However, in this hot press, the steel plate is heated to a high temperature of around 950 ° C before hot pressing, so scale (iron oxide) is generated on the surface of the steel plate and the scale peels off during hot pressing. There is a problem that the mold is damaged or the surface of the member after hot pressing is damaged. In addition, the scale remaining on the surface of the member also causes poor appearance and poor paint adhesion. For this reason, the scale on the surface of the member is usually removed by processing such as pickling or shot blasting, but this complicates the manufacturing process and causes a decrease in productivity. Furthermore, although excellent corrosion resistance is required for automobile undercarriage members and vehicle body structural members, hot press members manufactured by the above-described processes are not provided with a rust preventive film such as a plating layer. Therefore, the corrosion resistance is very insufficient.

  Therefore, there is a demand for hot press technology that can suppress the formation of scale during heating before hot pressing and improve the corrosion resistance of members after hot pressing. A steel sheet provided with a film and a hot pressing method using the same have been proposed. For example, Patent Document 2 discloses a hot-pressed member excellent in corrosion resistance in which a steel sheet coated with Zn or a Zn-based alloy is hot-pressed and a Zn-Fe-based compound or a Zn-Fe-Al-based compound is provided on the surface A manufacturing method is disclosed.

GB 1490535 Japanese Patent No. 3663145

  However, the hot-pressed member manufactured by the method described in Patent Document 2 may cause poor appearance and reduced coating adhesion due to scale generation, and may lead to corrosion resistance deterioration due to ZnO generation.

  It is an object of the present invention to provide a steel sheet for hot pressing that has excellent oxidation resistance capable of suppressing the formation of scale and ZnO during hot pressing, and a method for producing a hot pressed member using the same.

As a result of intensive studies on the steel sheet for hot pressing that is the above object, the present inventors have obtained the following knowledge.
i) Scale formation is likely to occur at local sites such as cracks originating from a defective portion of the plating layer or a Zn-Fe metal compound formed during heating by hot pressing.
ii) Scale and ZnO are likely to occur in a Zn-based plating layer with a melting point lower than 700 ° C.
iii) In order to suppress the formation of scale and ZnO, it is effective to form a plating layer containing 10 to 25% by mass of Ni having a high melting point and the balance being Zn and inevitable impurities.

The present invention has been made on the basis of such knowledge, and the steel sheet surface contains 10 to 25% by mass of Ni, the balance is made of Zn and inevitable impurities, and the amount of adhesion is 10 to 90 g / m ² . A steel sheet for hot pressing characterized by having a layer is provided.

  In the steel sheet for hot pressing according to the present invention, the plated layer further has at least one compound layer selected from a Si-containing compound layer, a Ti-containing compound layer, an Al-containing compound layer, and a Zr-containing compound layer. Is preferred.

  As the base steel sheet of the plating layer in the hot-press steel sheet of the present invention, in mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P: 0.1% or less, S: A steel plate containing 0.05% or less, Al: 0.1% or less, and N: 0.01% or less, with the balance being composed of Fe and inevitable impurities can be used. In this base steel sheet, in addition, by mass%, Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08% or Sb: 0.003 to 0.03% individually Or it is preferable to contain simultaneously.

The present invention also provides a method for producing a hot press member, characterized in that the hot press steel plate as described above is hot pressed after being heated to a temperature range of Ac ₃ transformation point to 1000 ° C. .

  According to the present invention, it is possible to manufacture a steel sheet for hot pressing that has excellent oxidation resistance and can suppress the formation of scale and ZnO during hot pressing. The hot press member manufactured by the hot press member manufacturing method of the present invention using the hot press steel plate of the present invention has a good appearance and has excellent paint adhesion and corrosion resistance. It is suitable for the underbody member and the vehicle body structural member.

1) Hot press steel sheet
1-1) Plating layer In the present invention, in order to suppress the formation of scale and ZnO during hot pressing, the surface of the steel plate contains 10 to 25% by mass or more of Ni, and the balance is made of Zn and inevitable impurities. Is provided. By setting the Ni content of the plating layer to 10 to 25% by mass, a γ phase having a high melting point of 881 ° C. having a crystal structure of Ni ₂ Zn ₁₁ , NiZn ₃ or Ni ₅ Zn ₂₁ is formed. Scale and ZnO formation reaction during heating can be minimized. Further, since no Zn—Fe metal compound is formed during heating, the generation of scale associated with the occurrence of cracks is also suppressed. Furthermore, since the plating layer remains as a γ phase even after the hot pressing is completed, excellent corrosion resistance is exhibited by the sacrificial anticorrosive effect of Zn. Note that the formation of the γ phase at a Ni content of 10 to 25% by mass does not necessarily match the equilibrium diagram of the Ni-Zn alloy, but this is a non-equilibrium reaction in the formation of the plating layer performed by electroplating. This is thought to be due to progress. The γ phase of Ni2Zn11, NiZn3, and Ni5Zn21 can be confirmed by an X-ray diffraction method or an electron diffraction method using TEM (Transmission Electron Microscopy). Moreover, although the γ phase is formed as described above by setting the Ni content of the plating layer to 10 to 25% by mass, some η phase may be mixed depending on the conditions of electroplating. At this time, in order to minimize the scale and ZnO formation reaction during heating, the η phase content is preferably 5% by mass or less. The η phase content is defined by the weight ratio of the η phase to the total weight of the plating layer, and can be quantified by, for example, the anodic dissolution method.

Coating weight per one surface of the plated layer, the sacrificial protection effect of Zn is less than 10 g / m @ 2 is not sufficiently exhibited, greater than 90 g / m ² when the effect is saturated, so increase the cost, 10～90G / and m ^2.

  A method for forming such a plating layer is not particularly limited, but a known electroplating method is preferable.

  When at least one compound layer selected from a Si-containing compound layer, a Ti-containing compound layer, an Al-containing compound layer, and a Zr-containing compound layer is further provided on the plating layer, excellent coating adhesion can be obtained. In order to obtain such an effect, the thickness of the compound layer is preferably 0.1 μm or more. However, if the thickness exceeds 3.0 μm, the compound layer may become brittle and decrease paint adhesion. It is preferable. More preferably, it is 0.4 to 2.0 μm.

  As the Si-containing compound, for example, silicone resin, lithium silicate, sodium silicate, colloidal silica, silane coupling agent and the like can be applied. As the Ti-containing compound, for example, a titanate such as lithium titanate or calcium titanate, a titanium coupling agent mainly containing a titanium alkoxide or a chelate-type titanium compound can be applied. As the Al-containing compound, for example, an aluminate such as sodium aluminate or calcium aluminate, an aluminum coupling agent mainly composed of an aluminum alkoxide or a chelate-type aluminum compound can be applied. As the Zr-containing compound, for example, a zirconate salt such as lithium zirconate or calcium zirconate, a zirconium coupling agent mainly composed of a zirconium alkoxide or a chelate-type zirconium compound can be applied.

  In order to form such a compound layer on the plating layer, after depositing on the plating layer at least one compound selected from the Si-containing compound, Ti-containing compound, Al-containing compound, Zr-containing compound, What is necessary is just to heat-dry without washing with water. The adhesion treatment of these compounds may be any of a coating method, a dipping method, and a spray method, and a roll coater, a squeeze coater, a die coater, or the like may be used. At this time, it is also possible to adjust the coating amount, make the appearance uniform, and make the thickness uniform by an air knife method or roll drawing method after the coating treatment, dipping treatment, and spraying treatment with a squeeze coater or the like. Moreover, it is preferable to perform heat drying so that the maximum reached temperature of a steel plate may be 40-200 degreeC. It is more preferable to carry out at 60 to 160 ° C.

  Further, in order to form such a compound layer on the plating layer, it contains at least one cation selected from Si, Ti, Al, and Zr, and is selected from among phosphate ions, fluoric acid ions, and fluoride ions. It is also possible to perform a reactive treatment in which a steel sheet having a plating layer is immersed in an acidic aqueous solution containing at least one kind of anion, and then wash with water or heat and dry without washing.

  Such a compound layer can contain an inorganic solid lubricant. This is because by including an inorganic solid lubricant, the dynamic friction coefficient during hot pressing can be reduced and press workability can be improved.

  Examples of inorganic solid lubricants include metal sulfides (such as molybdenum disulfide and tungsten disulfide), selenium compounds (such as molybdenum selenide and tungsten selenide), graphite, fluorides (such as graphite fluoride and calcium fluoride), Examples thereof include at least one selected from nitrides (boron nitride, silicon nitride, etc.), borax, mica, metal tin, and alkali metal sulfates (sodium sulfate, potassium sulfate, etc.). The content of the inorganic solid lubricant in the compound layer is preferably 0.1 to 20% by mass. This is because if 0.1% by mass or more, a lubricating effect is obtained, and if 20% by mass or less, paint adhesion does not deteriorate.

1-2) Base steel plate
In order to obtain a hot pressed member having a strength of 980 MPa or more, for example, as a base steel plate of a plating layer, in mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3%, P : Hot rolled steel sheet or cold rolled steel sheet having a component composition containing 0.1% or less, S: 0.05% or less, Al: 0.1% or less, N: 0.01% or less, the balance being Fe and inevitable impurities may be used. it can. The reason for limitation of each component element is demonstrated below. Here, “%” representing the content of a component means “% by mass” unless otherwise specified.

C: 0.15-0.5%
C is an element that improves the strength of steel. In order to increase the TS of a hot-pressed member to 980 MPa or more, the amount needs to be 0.15% or more. On the other hand, if the amount of C exceeds 0.5%, the blanking workability of the steel plate as the material will be significantly reduced. Therefore, the C content is 0.15 to 0.5%.

Si: 0.05-2.0%
Si, like C, is an element that improves the strength of steel. In order to increase the TS of a hot-pressed member to 980 MPa or more, the amount needs to be 0.05% or more. On the other hand, when the Si content exceeds 2.0%, the occurrence of surface defects called red scale during hot rolling is remarkably increased, the rolling load is increased, and the ductility of the hot-rolled steel sheet is deteriorated. Furthermore, if the Si content exceeds 2.0%, the plating processability may be adversely affected when a plating process for forming a plating film mainly composed of Zn or Al on the steel sheet surface is performed. Therefore, the Si content is 0.05 to 2.0%.

Mn: 0.5-3%
Mn is an effective element for improving the hardenability by suppressing the ferrite transformation, and also an element effective for lowering the heating temperature before hot pressing because it lowers the Ac ₃ transformation point. is there. In order to exhibit such an effect, the amount needs to be 0.5% or more. On the other hand, when the amount of Mn exceeds 3%, segregation occurs and the uniformity of the characteristics of the raw steel plate and the hot press member decreases. Therefore, the amount of Mn is 0.5 to 3%.

P: 0.1% or less
When the amount of P exceeds 0.1%, segregation occurs and the uniformity of the characteristics of the raw steel plate and hot-pressed member decreases, and the toughness also decreases significantly. Therefore, the P content is 0.1% or less.

S: 0.05% or less
When the amount of S exceeds 0.05%, the toughness of the hot pressed member decreases. Therefore, the S content is 0.05% or less.

Al: 0.1% or less
If the Al content exceeds 0.1%, blanking workability and hardenability of the steel sheet will be reduced. Therefore, the Al content is 0.1% or less.

N: 0.01% or less
If the N content exceeds 0.01%, an AlN nitride is formed during hot rolling or heating before hot pressing, and the blanking workability and hardenability of the raw steel sheet are reduced. Therefore, the N content is 0.01% or less.

  The balance is Fe and inevitable impurities, but for the following reasons, at least one selected from Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08%, Sb: 0.003 to 0.03 % Are preferably contained individually or simultaneously.

Cr: 0.01-1%
Cr is an element effective for strengthening steel and improving hardenability. In order to exhibit such an effect, the Cr content is preferably 0.01% or more. On the other hand, if the Cr content exceeds 1%, the cost is significantly increased, so the upper limit is preferably 1%.

Ti: 0.2% or less
Ti is an element effective for strengthening steel and improving toughness by refining. It is also an element effective for forming a nitride in preference to B, which will be described next, and exhibiting the effect of improving hardenability by solid solution B. However, if the amount of Ti exceeds 0.2%, the rolling load during hot rolling is extremely increased and the toughness of the hot pressed member is lowered, so the upper limit is preferably 0.2%.

B: 0.0005-0.08%
B is an element effective for improving the hardenability during hot pressing and toughness after hot pressing. In order to exhibit such an effect, the B content is preferably 0.0005% or more. On the other hand, if the amount of B exceeds 0.08%, the rolling load during hot rolling is extremely increased, and the martensite phase and bainite phase occur after hot rolling, resulting in cracks in the steel sheet, so the upper limit is It is preferable to set it to 0.08%.

Sb: 0.003-0.03%
Sb has an effect of suppressing a decarburized layer generated in the steel sheet surface layer portion between the time when the steel plate is heated before hot pressing and the time when the steel plate is cooled by a series of processes of hot pressing. In order to exhibit such an effect, the amount needs to be 0.003% or more. On the other hand, if the Sb content exceeds 0.03%, the rolling load increases and the productivity decreases. Accordingly, the Sb content is preferably 0.003 to 0.03%.

2) hot-press steel sheet of the present invention produced the method above hot pressing member is pressed between heated after heat temperature range of Ac ₃ transformation point to 1000 ° C. the hot press member. The reason for heating above the Ac ₃ transformation point before hot pressing is to form a hard phase such as a martensite phase by rapid cooling during hot pressing, thereby increasing the strength of the member. The upper limit of the heating temperature is set to 1000 ° C. because when the temperature exceeds 1000 ° C., a large amount of ZnO is generated on the surface of the plating layer. In addition, the heating temperature here means the highest temperature reached of the steel sheet.

  The average rate of temperature rise during heating before hot pressing is not particularly limited, but is preferably 2 to 200 ° C./s, for example. Formation of ZnO on the surface of the plating layer and generation of local scale in the defective portion of the plating layer increase as the high-temperature residence time during which the steel sheet is exposed to high-temperature conditions increases. . Further, the holding time at the maximum plate temperature is not particularly limited, but it is preferable to shorten the holding time for the same reason as described above, preferably 300 s or less, more preferably 120 s or less, more preferably 10 s. The following.

  Examples of the heating method before hot pressing include heating by an electric furnace or a gas furnace, flame heating, energization heating, high frequency heating, induction heating, and the like.

As a base steel sheet, in mass%, C: 0.23%, Si: 0.25%, Mn: 1.2%, P: 0.01%, S: 0.01%, Al: 0.03%, N: 0.005%, Cr: 0.2%, Ti: A cold-rolled steel sheet containing 0.02%, B: 0.0022%, Sb: 0.008%, the balance being composed of Fe and inevitable impurities, an Ac ₃ transformation point of 820 ° C, and a thickness of 1.6 mm is used. It was. The surface of this cold-rolled steel sheet has a current density of 5 in a plating bath containing 200 g / L nickel sulfate hexahydrate and 10 to 100 g / L zinc sulfate heptahydrate at a pH of 1.5 and a temperature of 50 ° C. Steel plate having plating layers with different Ni content (the balance is Zn and unavoidable impurities), adhesion amount, and η phase content as shown in Table 1 after applying electroplating treatment to -100 A / dm ² No. 1 to 19 were produced. In addition, for comparison, hot-dip plated steel sheet (GI), alloyed hot-dip zinc-plated steel sheet (GA), hot-dip Zn-5% Al-plated steel sheet (GF), hot-dip Zn-55 Steel plates Nos. 20 to 24 were produced as% Al-plated steel plates (GL) and cold-rolled steel plates without plating layers.

The steel plates No. 1 to 24 thus obtained were heated under the heating conditions shown in Table 1 by an electric furnace or direct energization, and then sandwiched between Al molds and cooled at a cooling rate of 50 ° C./s. The oxidation resistance shown was evaluated.
Oxidation resistance: After heating under the heating conditions shown in Table 1, the weight of the steel sheet was measured, and the change in weight before heating was measured. Here, the weight change is the sum of the weight increase due to the scale and ZnO generation and the weight decrease due to the scattering of the generated ZnO, but the smaller the absolute value, the better the oxidation resistance. If ◎ or ○, the object of the present invention was satisfied.
A: Absolute value of weight change ≦ 3 g / m ²
○: 3 g / m ² <absolute value of weight change ≦ 5 g / m ²
×: 5 g / m ² <absolute value of weight change The results are shown in Table 1. It can be seen that the steel plates No. 1 to 16 according to the present invention all have a small absolute value of weight change and are excellent in oxidation resistance.

  In this example, processing by hot pressing was not actually performed, but as described above, the oxidation resistance depends on changes in the plating layer due to heating before hot pressing, particularly the behavior of Zn in the plating layer. Therefore, the oxidation resistance of the hot press member can be evaluated based on the result of this example.

  By the same method as in Example 1, plating layers having different Ni content, adhesion amount, and η phase content were formed on the surface of the base steel plate similar to Example 1. Thereafter, on the plating layer, a composition comprising any of the following compounds containing Si, a Ti-containing compound, an Al-containing compound, a Zr-containing compound, and Si and a Zr-containing compound (solid content ratio 15 After coating, the steel sheet is dried under the condition that the ultimate steel sheet temperature is 140 ° C., and the Si-containing compound layer, Ti-containing compound layer, Al-containing compound layer, Zr-containing compound layer, Si having different thicknesses shown in Tables 2 and 3 And any one of the Zr-containing compound layers were formed, and steel plates No. 1 to 32 were produced.

  The following compounds were used as Si-containing compounds, Ti-containing compounds, Al-containing compounds, and Zr-containing compounds.

Silicone resin: KR-242A manufactured by Shin-Etsu Chemical Co., Ltd.
Lithium silicate: manufactured by Nissan Chemical Industries, Ltd. Lithium silicate 45
Colloidal silica: Snowtex OS made by Nissan Chemical Industries
Silane coupling agent: KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.
Titanium coupling agent: ORGATICS TA-22 manufactured by Matsumoto Fine Chemical Co., Ltd.
Lithium titanate: manufactured by Titanium Industry Co., Ltd. Lithium titanate sodium aluminate: manufactured by Asahi Chemical Industry Co., Ltd. NA-170
Aluminum coupling agent: Ajinomoto Fine Techno Co., Ltd. Pre-act AL-M
Zirconium acetate: Sanei Kako Co., Ltd. Zirconium acetate Zirconium coupling agent: Matsumoto Fine Chemical Co., Ltd. ORGATICS ZA-65
The solvent in the case of using a silicone resin as the compound was 55:45 (mass ratio) thinner of ethylene glycol monobutyl ether: petroleum naphtha. Moreover, the solvent in the case of using things other than a silicone resin as a compound was deionized water.

The steel plates No. 1 to 32 shown in Tables 2 and 3 having a plating layer and a compound layer were sequentially heated on the surface in the heating conditions shown in Tables 2 and 3 by an electric furnace or direct energization. After that, it was sandwiched between Al molds and cooled at a cooling rate of 50 ° C./s, and the same oxidation resistance evaluation as in Example 1 and the following coating adhesion evaluation were performed.
Paint adhesion: A sample was taken from the heat-treated steel sheet, subjected to chemical conversion treatment under standard conditions using PB-SX35 manufactured by Nihon Parkerizing Co., Ltd., then applied with 170 electrodeposited paint GT-10HT gray manufactured by Kansai Paint Co., Ltd. A coating test piece was prepared by forming a film with a thickness of 20 μm under baking conditions of 20 ° C. for 20 minutes. Then, a cut that reaches the steel substrate of the grid pattern (10 x 10 pieces, 1 mm interval) with a cutter knife is put on the surface that has been subjected to chemical conversion treatment and electrodeposition coating of the prepared test piece, and is attached with an adhesive tape. A cross-cut tape peeling test was conducted. Evaluation was made according to the following criteria, and ◎ and ○ were considered excellent in paint adhesion.
A: No peeling B: Separation at 1 to 10 grids Δ: Separation at 11 to 30 grids ×: Peeling at 31 or more grids Tables 2 and 3 show the results. By providing the compound layer, it can be seen that in addition to oxidation resistance, the coating adhesion is also excellent.

  In addition, although the process by a hot press is not actually performed in a present Example, the coating adhesiveness of a hot press member can also be evaluated by the result of a present Example similarly to oxidation resistance.

Claims (4)

A steel plate surface containing 10 to 25% by mass of Ni, the balance being Zn and inevitable impurities, and an adhesion amount of 10 to 90 g / m ² (however, the surface of the plating layer is mainly composed of Zn and Mn Oxide layer containing at least 1% by mass, a barrier layer made of a zinc oxide layer having a thickness of 0.01 to 5.0 μm, and a ZnO layer having a ZnO layer of 10 mgm ⁻² or more in terms of Zn) The η phase content of the plating layer is 5% by mass or less, and the base steel sheet of the plating layer is by mass%, C: 0.15-0.5%, Si: 0.05-2.0%, Mn: 0.5-3% , P: 0.01 to 0.1%, S: 0.05% or less, Al: 0.1% or less, N: 0.01% or less, the balance having a component composition consisting of Fe and inevitable impurities, hot press characterized by Steel plate.   The base steel sheet of the plating layer further contains at least one selected from Cr: 0.01 to 1%, Ti: 0.2% or less, B: 0.0005 to 0.08% by mass%. 1. A steel sheet for hot pressing as described in 1.   The steel sheet for hot press according to claim 1 or 2, wherein the base steel sheet of the plating layer further contains Sb: 0.003 to 0.03% by mass. A method for producing a hot press member, comprising: hot pressing the steel sheet for hot pressing according to any one of claims 1 to 3 to a temperature range of Ac ₃ transformation point to 1000 ° C. .