JP5888268B2 - Method for producing high-strength hot-dip galvanized steel sheet and high-strength hot-dip galvanized steel sheet - Google Patents

Description

  The present invention is a method for producing a high-strength hot-dip galvanized steel sheet with excellent plating appearance, corrosion resistance, high-peeling peel-off resistance and workability using a high-strength steel sheet containing Si and Mn, and high-strength melting. It relates to a galvanized steel sheet.

  In recent years, in the fields of automobiles, home appliances, building materials and the like, surface-treated steel sheets imparted with rust resistance to raw steel sheets, particularly hot-dip galvanized steel sheets and galvannealed steel sheets have been widely used. In addition, from the viewpoint of improving the fuel efficiency of automobiles and improving the collision safety of automobiles, there is an increasing demand for reducing the thickness of the vehicle body by increasing the strength of the vehicle body material and reducing the weight of the vehicle body. Therefore, application of high-strength steel sheets to automobiles is being promoted.

  In general, a hot dip galvanized steel sheet uses a thin steel sheet obtained by hot rolling or cold rolling a slab as a base material. Manufactured by recrystallization annealing and hot dip galvanizing. In the case of an alloyed hot-dip galvanized steel sheet, it is manufactured after further hot-dip galvanizing treatment.

  Here, there are DFF type (direct flame type), NOF type (non-oxidation type), all radiant tube type, etc. as the heating furnace type of CGL annealing furnace. The construction of CGLs equipped with an all-radiant tube type heating furnace is increasing for the reason that it is possible to produce high-quality plated steel sheets at low cost due to difficulty in carrying out the process. However, unlike the DFF type (direct flame type) and NOF type (non-oxidation type), the all-radiant tube type heating furnace does not have an oxidation step immediately before annealing, so a steel plate containing an easily oxidizable element such as Si or Mn. Is disadvantageous in terms of securing plating properties.

  As a method for producing a hot-dip galvanized steel sheet using a high-strength steel sheet containing a large amount of Si and Mn as a base material, Patent Document 1 discloses a technique for annealing and plating at a recrystallization temperature of -900 ° C. Patent Document 2 discloses a technique for annealing and plating at 750 to 900 ° C. Patent Document 3 discloses a technique of annealing and plating at 800 to 850 ° C. However, in the case of a high-strength steel sheet containing a large amount of Si and Mn, when annealing is performed at a high temperature exceeding 750 ° C., Si and Mn in the steel are selectively oxidized, and an oxide is formed on the surface of the steel sheet. There is a concern that defects such as non-plating occur.

  Furthermore, Patent Document 4 and Patent Document 5 disclose a technique for internally oxidizing the surface layer of the ground iron by defining the heating temperature in the reduction furnace with an expression represented by the partial pressure of water vapor and increasing the dew point. However, since the area for controlling the dew point is premised on the entire inside of the furnace, it is difficult to control the dew point, and stable operation is difficult. In addition, the production of alloyed hot-dip galvanized steel sheets under unstable dew point control has been observed in the distribution of internal oxides formed on the base steel sheet, and is plated in the longitudinal and width directions of the steel strip. There are concerns that defects such as wettability and uneven alloying may occur.

  Furthermore, recently, the application of high-strength hot-dip galvanized steel sheets and high-strength alloyed hot-dip galvanized steel sheets to places where processing is severe has progressed, and the anti-plating resistance characteristics during high processing have become important. Yes. Specifically, it is required to suppress plating peeling at the processed part when the plated steel sheet is bent at an angle of more than 90 ° and bent at an acute angle or when the steel sheet is processed by impact.

  In order to satisfy these characteristics, not only a large amount of Si or Mn is added to the steel to ensure the desired steel sheet structure, but also directly under the plating layer, which may be the starting point of cracks during high processing. More advanced control of the structure and structure of the surface steel layer is required. However, such control is difficult in the prior art, and CGL is equipped with an all-radiant tube type heating furnace in the annealing furnace, and it is excellent in anti-plating resistance at high processing using a high-strength steel sheet containing Si and Mn as a base material. A hot-dip galvanized steel sheet could not be produced.

JP 2009-287114 A JP 2008-24980 A JP 2010-150660 A JP 2004-323970 A JP 2004-315960 A

  The present invention has been made in view of such circumstances, and uses a steel sheet containing Si and Mn as a base material, and has high strength melting excellent in plating appearance, corrosion resistance, plating peeling resistance during high processing and workability. An object of the present invention is to provide a method for producing a galvanized steel sheet and a high-strength hot-dip galvanized steel sheet.

The present inventors examined a method for solving the problem by a new method not confined to the conventional idea. As a result, by controlling the structure and structure of the surface layer of the underlying steel plate directly under the plating layer, which may be the starting point of cracks during high processing, the plating appearance and anti-plating resistance during high processing It was found that a high-strength hot-dip galvanized steel sheet having excellent properties can be obtained. Specifically, after making the Fe-based oxide adhere to the base steel plate surface in an O amount of 0.08 to 1.5 g / m ² on one side, the maximum steel plate temperature in the annealing furnace is set to 600 ° C. or higher and 750 ° C. The steel sheet is annealed and hot dip galvanized in a continuous hot dip galvanizing facility at a temperature not higher than ° C. By performing such treatment, selective surface oxidation can be suppressed, surface concentration can be suppressed, and a high-strength hot-dip galvanized steel sheet excellent in plating appearance and plating peeling resistance during high processing can be obtained. It will be. In addition, having excellent plating appearance means having an appearance in which non-plating and alloying unevenness are not recognized.
And the high-strength hot-dip galvanized steel sheet obtained by the above method has Fe, Si, Mn, Al, P, and B in the steel sheet surface layer part within 100 μm from the surface of the base steel sheet in the steel sheet surface layer part directly under the plating layer. Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb, Ta, W, V, and at least one oxide selected from 0.010 to 0.100 g / m ² per side is formed. In the region from directly below the plating layer to 10 μm, the structure and structure are such that an oxide containing Mn is precipitated in grains within 1 μm from the grain boundary of the underlying steel sheet. As a result, stress relaxation and prevention of cracking at the time of bending in the steel sheet surface layer can be realized, and the plating appearance and plating peeling resistance at the time of high processing are excellent.

  The present invention is based on the above findings, and features are as follows.

[1] By mass%, C: 0.03 to 0.35%, Si: 0.01 to 0.50%, Mn: 3.6 to 8.0%, Al: 0.001 to 1.000% , P ≦ 0.10%, S ≦ 0.010%, and a zinc plating layer having a plating adhesion amount of 20 to 120 g / m ^{2 on} one side on the surface of the steel plate, the balance being Fe and inevitable impurities. A method for producing a high-strength hot-dip galvanized steel sheet having an Fe-based oxide deposited on the surface of the underlying steel sheet in an O amount of 0.08 to 1.5 g / m ² on one side, followed by continuous hot-dip galvanizing A method for producing a high-strength hot-dip galvanized steel sheet, characterized in that the steel sheet is subjected to annealing and hot-dip galvanizing treatment at a maximum steel plate temperature of 600 ° C. or higher and 750 ° C. or lower in an annealing furnace.
[2] In the above [1], the steel sheet has a component composition in mass%, and further B: 0.001 to 0.005%, Nb: 0.005 to 0.050%, Ti: 0.005. ~ 0.050%, Cr: 0.001-1.000%, Mo: 0.05-1.00%, Cu: 0.05-1.00%, Ni: 0.05-1.00%, Sn: 0.001 to 0.20%, Sb: 0.001 to 0.20%, Ta: 0.001 to 0.10%, W: 0.001 to 0.10%, V: 0.001 A method for producing a high-strength hot-dip galvanized steel sheet, comprising one or more elements selected from 0.10%.
[3] In the above [1] or [2], after the hot dip galvanizing treatment, the steel plate is further heated to a temperature of 450 ° C. or higher and 600 ° C. or lower to perform alloying treatment, and the Fe content of the plating layer is 8 to A method for producing a high-strength hot-dip galvanized steel sheet, characterized by being in the range of 14% by mass.
[4] Fe, Si, Mn, Al, P, which is produced by any one of the production methods described in [1] to [3] above the surface layer portion of the steel plate within 100 μm from the surface of the underlying steel plate immediately below the galvanized layer. At least one oxide selected from B, Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb, Ta, W, and V is 0.010 to 0.100 g / m per side in total. ^In addition, in a region within 10 μm from the surface of the underlying steel sheet immediately below the plating layer, an oxide containing Mn is present in grains within 1 μm from the grain boundary of the underlying steel plate, and high strength melting Galvanized steel sheet.

  In the present invention, the high strength hot dip galvanized steel sheet has a tensile strength TS of 590 MPa or more. The high-strength hot-dip galvanized steel sheet of the present invention includes a plated steel sheet (hereinafter sometimes referred to as GI) that is not subjected to alloying after the hot-dip galvanizing process, and a plated steel sheet (hereinafter referred to as GA) that is subjected to the alloying process. In some cases). In addition, the Fe-based oxide means that the oxide of Fe is 50% or more of the oxide constituent elements and includes oxides of elements other than Fe contained in the steel sheet.

  ADVANTAGE OF THE INVENTION According to this invention, the high intensity | strength hot-dip galvanized steel plate excellent in plating external appearance, corrosion resistance, the plating peeling resistance at the time of high processing, and workability is obtained.

  Hereinafter, the present invention will be specifically described. In the following description, the content of each element of the steel component composition and the unit of the content of each element of the plating layer component composition are all “mass%”, and hereinafter, simply “%” unless otherwise specified. Show.

  First, the annealing atmosphere conditions etc. which determine the structure of the surface of the base steel plate immediately under the plating layer, which is the most important requirement in the present invention, will be described.

After depositing the Fe-based oxide on the surface of the underlying steel sheet in an O amount of 0.08 to 1.5 g / m ² per side, the maximum temperature reached in the annealing furnace in the continuous hot dip galvanizing facility is 600 ° C or higher. By applying annealing and hot dip galvanizing treatment to the steel sheet at 750 ° C or lower, an appropriate amount of oxides of oxidizable elements (Si, Mn, etc.) (hereinafter referred to as internal oxides) exist within the surface of the steel sheet within 100 μm. Thus, it is possible to suppress selective surface oxidation (hereinafter referred to as surface concentration) in the steel sheet surface layer of Si, Mn, etc. in steel, which deteriorates the wettability of the hot dip galvanizing and steel sheet after annealing.

The reason why the Fe-based oxide layer is present at 0.08 to 1.5 g / m ² per one surface on the surface of the underlying steel plate before annealing is as follows. If the amount of O is less than 0.08 g / m ² , the surface concentration of alloy elements such as Si and Mn in the steel cannot be prevented, and the plating properties deteriorate. On the other hand, if the amount of O exceeds 1.5 g / m ² , in the subsequent annealing step, O (oxygen) in the surface layer remains without being completely reduced, which causes a decrease in the alloying rate in the plating alloying step. The plating adhesion will deteriorate.
As a method for attaching the Fe-based oxide layer to the surface of the underlying steel plate, the heating zone is controlled to an atmosphere where Fe is oxidized during annealing, and the steel plate temperature is raised to 400 ° C. to 700 ° C. in that atmosphere. The method of performing is mentioned. The method is not limited to the above. For example, a method such as pre-plating may be used.

The reason why the maximum temperature of the steel sheet in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower is as follows. In the temperature range below 600 ° C., surface enrichment and internal oxidation that cause problems such as occurrence of non-plating, deterioration of corrosion resistance and deterioration of plating peeling resistance do not occur, but a good material cannot be obtained. Therefore, the temperature range in which the effects of the present invention are manifested is 600 ° C. or higher. On the other hand, in the temperature range above 750 ° C., even when O is present in an amount of 0.08 g / m ² or more before annealing, surface concentration becomes remarkable, and non-plating occurs, corrosion resistance deteriorates, plating peel resistance deteriorates, etc. Become intense. Furthermore, in terms of materials, the effect of balance between strength and ductility is saturated in a temperature range where both TS and El exceed 750 ° C. From the above, the maximum reached temperature of the steel sheet is 600 ° C. or higher and 750 ° C. or lower.

  There is no particular limitation on the dew point when the Fe-based oxide is adhered to the surface of the underlying steel sheet and the dew point in the temperature range where the steel sheet temperature is 600 ° C. or higher and 750 ° C. or lower. Controlling to below -80 ° C may cause an increase in cost. If it exceeds 80 ° C., the amount of Fe oxidation increases, and there is a concern about deterioration in the annealing furnace and rolls. Therefore, -80 ° C or higher and 80 ° C or lower is preferable.

Next, the steel component composition of the high-strength hot-dip galvanized steel sheet that is the subject of the present invention will be described.
C: 0.03-0.35%
C improves workability by forming martensite or the like as a steel structure. For that purpose, 0.03% or more is necessary. On the other hand, if it exceeds 0.35%, the weldability deteriorates. Therefore, the C content is 0.03% or more and 0.35% or less.

Si: 0.01 to 0.50%
Si is an element effective for strengthening steel and obtaining a good material, but it is an easily oxidizable element, which is disadvantageous for plating properties and should be avoided as much as possible. However, about 0.01% is inevitably contained in the steel, and in order to reduce to less than this, the cost increases, so 0.01% is made the lower limit. On the other hand, when it exceeds 0.50%, it becomes difficult to improve the plating peel resistance at the time of high processing. Therefore, the Si amount is set to 0.01% or more and 0.50% or less.

Mn: 3.6-8.0%
Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 3.6% or more. On the other hand, if it exceeds 8.0%, it becomes difficult to ensure weldability and plating adhesion, and to ensure a balance between strength and ductility. Therefore, the Mn content is 3.6% or more and 8.0% or less.

Al: 0.001-1.000%
Al is added for the purpose of deoxidizing molten steel, but if the content is less than 0.001%, the purpose is not achieved. The effect of deoxidation of molten steel is obtained at 0.001% or more. On the other hand, if it exceeds 1.000%, the cost increases. Therefore, the Al amount is set to 0.001% or more and 1.000% or less.

P ≦ 0.10%
P is one of the elements inevitably contained, and in order to make it less than 0.005%, there is a concern about an increase in cost, so 0.005% or more is desirable. On the other hand, if P exceeds 0.10%, weldability deteriorates. Furthermore, the surface quality deteriorates. Also, the plating adhesion deteriorates during non-alloying treatment, and the desired degree of alloying cannot be achieved unless the alloying treatment temperature is increased during alloying treatment. Also, if the alloying temperature is raised to achieve the desired degree of alloying, the ductility deteriorates and at the same time the adhesion of the alloyed plating film deteriorates, so the desired degree of alloying, good ductility, and alloyed plating film Cannot be achieved. Accordingly, the P content is preferably 0.10% or less, and the lower limit is preferably 0.005%.

S ≦ 0.010%
S is one of the elements inevitably contained. The lower limit is not specified, but if it is contained in a large amount, weldability deteriorates, so the content is made 0.010% or less.

In order to control the balance between strength and ductility, B: 0.001 to 0.005%, Nb: 0.005 to 0.050%, Ti: 0.005 to 0.050%, Cr: 0.001 One or more elements selected from -1.000%, Mo: 0.05-1.00%, Cu: 0.05-1.00%, Ni: 0.05-1.00% are required It may be added depending on.
The reason for limiting the appropriate addition amount in the case of adding these elements is as follows.

B: 0.001 to 0.005%
When B is less than 0.001%, it is difficult to obtain an effect of promoting quenching. On the other hand, if it exceeds 0.005%, the plating adhesion deteriorates. Therefore, when it contains, B amount shall be 0.001% or more and 0.005% or less. However, when it is judged that it is not necessary to improve the mechanical properties, it is not necessary to add it.

Nb: 0.005 to 0.050%
If Nb is less than 0.005%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Mo. On the other hand, if it exceeds 0.050%, cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.050% or less.

Ti: 0.005 to 0.050%
If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.050%, the plating adhesion deteriorates. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.050% or less.

Cr: 0.001-1.000%
When Cr is less than 0.001%, it is difficult to obtain a hardenability effect. On the other hand, if it exceeds 1.000%, the surface of Cr is concentrated, so that the plating adhesion and weldability deteriorate. Therefore, when it contains, Cr content shall be 0.001% or more and 1.000% or less.

Mo: 0.05-1.00%
If Mo is less than 0.05%, it is difficult to obtain the effect of adjusting the strength and the effect of improving the plating adhesion at the time of composite addition with Nb, Ni or Cu. On the other hand, if it exceeds 1.00%, cost increases. Therefore, when it contains, Mo amount shall be 0.05% or more and 1.00% or less.

Cu: 0.05-1.00%
If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual γ phase and the effect of improving the plating adhesion when combined with Ni or Mo. On the other hand, if it exceeds 1.00%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.00% or less.

Ni: 0.05-1.00%
When Ni is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual γ phase and the effect of improving the plating adhesion upon the combined addition of Cu and Mo. On the other hand, if it exceeds 1.00%, cost increases. Therefore, when contained, the Ni content is 0.05% or more and 1.00% or less.

Sn: 0.001 to 0.20%, Sb: 0.001 to 0.20%
Sn or Sb can be contained from the viewpoint of suppressing decarburization in the region of several tens of microns on the surface of the steel sheet caused by nitriding, oxidation, or oxidation of the steel sheet surface. By suppressing such nitriding and oxidation, a reduction in the amount of martensite produced on the steel sheet surface is prevented, and fatigue characteristics and surface quality are improved. From the viewpoint of suppressing nitriding and oxidation, when Sn or Sb is contained, the content is made 0.001% or more. If it exceeds 0.20%, the toughness is deteriorated. Therefore, the content is preferably 0.20% or less.

Ta: 0.001 to 0.10%
Ta contributes to high strength and high yield ratio (YR) by forming C and N together with carbides and carbonitrides. Furthermore, Ta has the effect of refining the hot-rolled sheet structure, and since the ferrite grain size after cold rolling and annealing is refined, the increase in the amount of C segregation at the grain boundary accompanying the increase in grain boundary area A high seizure hardening amount (BH amount) can be obtained. From such a viewpoint, 0.001% or more of Ta can be contained. On the other hand, the content of excess Ta exceeding 0.10% not only increases the raw material cost but also may hinder the formation of martensite in the cooling process after annealing, and further precipitates in the hot-rolled sheet. TaC increases the deformation resistance during cold rolling and may make it difficult to produce a stable actual machine. When TaC is contained, the content is made 0.10% or less.

W: 0.001% to 0.10%
By adding W in combination with Si and Mn, there is an effect of suppressing the formation of a Γ phase and improving plating adhesion. Such an effect is recognized by containing W: 0.001% or more. On the other hand, even if it contains exceeding 0.10%, an effect will be saturated and the effect corresponding to content cannot be expected, but it becomes economically disadvantageous. As mentioned above, when it contains W, it is set as 0.001% or more and 0.10% or less.

V: 0.001 to 0.10%
V is an element that forms carbonitrides and has the effect of increasing the strength of steel by the precipitation effect, and can be contained as necessary. Such an effect is recognized when the content of V is 0.001% or more. On the other hand, when it contains exceeding 0.10%, it will become high strength too much and ductility will deteriorate. From the above, when V is contained, the content is made 0.001% or more and 0.10% or less.

  The balance other than the above is Fe and inevitable impurities. Even if elements other than the elements described above are contained, the present invention is not adversely affected, and the upper limit is made 0.1%.

  Next, the manufacturing method of the high-strength hot-dip galvanized steel sheet of the present invention and the reason for limitation will be described.

The steel having the above chemical components is hot-rolled and then cold-rolled to obtain a steel plate, and then subjected to annealing and hot-dip galvanizing treatment in a continuous hot-dip galvanizing facility. At this time, in the present invention, after the Fe-based oxide is deposited on the surface of the base steel plate in an amount of O of 0.08 to 1.5 g / m ² on one side, the inside of the annealing furnace in the continuous hot dip galvanizing equipment The steel sheet is subjected to annealing and hot dip galvanizing treatment at a maximum temperature of 600 ° C. or higher and 750 ° C. or lower. This is the most important requirement in the present invention. Thus, by allowing Fe-based oxides to be present on the surface of the underlying steel plate before annealing, Si, Mn, etc., which are easily oxidizable elements during annealing, are internally oxidized in advance, and the activity of Si and Mn in the surface layer portion of the underlying steel plate Decreases. And the external oxidation of these elements is suppressed, and as a result, plating property and plating peeling resistance are improved.

Hot rolling Usually, it can be performed on the conditions performed.

It is preferable to perform a pickling treatment after hot pickling. The black scale formed on the surface in the pickling process is removed, and then cold-rolled. The pickling conditions are not particularly limited.

Cold rolling is preferably performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, when the rolling reduction exceeds 80%, the steel sheet is a high-strength steel plate, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the plating characteristics are deteriorated.

After cold-rolling the steel sheet, the Fe-based oxide was deposited on the surface of the base steel sheet in an amount of O of 0.08 to 1.5 g / m ² on one side, and then in an annealing furnace in a continuous hot dip galvanizing facility. The steel sheet is subjected to annealing and hot dip galvanizing treatment at a maximum temperature of 600 ° C. or higher and 750 ° C. or lower.

In the annealing furnace, a heating process is performed in which the steel sheet is heated to a predetermined temperature in a preceding heating zone, and a soaking process is performed in which the temperature is maintained at a predetermined temperature for a predetermined time in a subsequent soaking zone.
And as above-mentioned, the steel plate highest reached temperature in an annealing furnace is 600 degreeC or more and 750 degrees C or less. The dew point in the annealing furnace atmosphere in the temperature range of 600 ° C. or higher and 750 ° C. or lower is not particularly limited. Preferably it is -80 degreeC-80 degreeC.

If the volume fraction of H _{2 in} the atmosphere is less than 1%, the activation effect by reduction cannot be obtained, and the plating peel resistance deteriorates. The upper limit is not particularly specified, but if it exceeds 50%, the cost increases and the effect is saturated. Therefore, the volume fraction of H ₂ is preferably 1% or more and 50% or less. The balance consists of N ₂ and inevitable impurity gas. Other gas components such as H ₂ O, CO ₂ and CO may be contained as long as the effects of the present invention are not impaired.

Further, when compared under the same annealing conditions, the surface enrichment amount of Si and Mn increases in proportion to the amount of Si and Mn in the steel. In the case of the same steel type, in a relatively high oxygen potential atmosphere, since Si and Mn in the steel move to internal oxidation, the amount of surface enrichment decreases as the oxygen potential in the atmosphere increases. Therefore, when the amount of Si and Mn in steel is large, it is necessary to increase the oxygen potential in the atmosphere by increasing the dew point.
The hot dip galvanizing treatment can be performed by a conventional method.

Next, an alloying treatment is performed as necessary.
When the alloying treatment is performed subsequent to the hot dip galvanizing treatment, the hot dip galvanizing treatment is performed, and then the steel plate is heated to 450 ° C. or higher and 600 ° C. or lower to perform the alloying treatment, and the Fe content of the plating layer is 8 to 14%. It is preferable to do so. If it is less than 8%, unevenness in alloying and flaking properties deteriorate. On the other hand, if it exceeds 14%, the plating peel resistance deteriorates.

As described above, the high-strength hot-dip galvanized steel sheet of the present invention is obtained. The high-strength hot-dip galvanized steel sheet of the present invention has a galvanized layer having a plating adhesion amount of 20 to 120 g / m ^{2 on} one surface of the steel sheet. If it is less than 20 g / m ² , it becomes difficult to ensure corrosion resistance. On the other hand, when it exceeds 120 g / m ² , the plating peel resistance deteriorates.

And it has the characteristic in the structure of the base steel plate surface just under a plating layer as follows.
On the surface layer portion of the steel plate within 100 μm from the surface of the underlying steel plate immediately below the galvanized layer, Fe, Si, Mn, Al, P, and further B, Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb One or more oxides selected from Ta, W, and V are formed in a total amount of 0.010 to 0.100 g / m ² per side. Further, in the region immediately below the plating layer from the surface of the underlying steel plate to 10 μm, an oxide containing Mn is present in grains within 1 μm from the grain boundary of the underlying steel plate.

In hot-dip galvanized steel sheets with Si and a large amount of Mn added to the steel, in order to satisfy the anti-plating resistance at the time of high processing, it is directly under the plating layer that may be the starting point of cracking at the time of high processing. It is necessary to control the structure and structure of the surface steel sheet surface layer to a higher degree. Therefore, in the present invention, first, in order to ensure plating properties, an Fe-based oxide is present on the surface of the base steel plate before annealing to increase the oxygen potential during annealing. As a result, by increasing the oxygen potential, easily oxidizable elements such as Si and Mn are internally oxidized in advance immediately before plating, and the activities of Si and Mn in the surface layer of the underlying steel sheet are lowered. And the external oxidation of these elements is suppressed, and as a result, plating property and plating peeling resistance are improved. Furthermore, this improvement effect is obtained by applying Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, and a steel plate surface layer portion within 100 μm from the surface of the base steel plate directly below the galvanized layer. At least one oxide selected from Ni, Sn, Sb, Ta, W, and V is present at 0.010 g / m ² or more per side. On the other hand, if it exceeds 0.100 g / m ² , it becomes a starting point for cracking during processing and the plating peelability deteriorates, so the upper limit is made 0.100 g / m ² .

Moreover, when an internal oxide exists only in a grain boundary and does not exist in a grain, the grain boundary diffusion of an easily oxidizable element in steel can be suppressed, but the intragranular diffusion may not be sufficiently suppressed. Therefore, in the present invention, as described above, after the Fe-based oxide is deposited on the surface of the underlying steel plate in an amount of O of 0.08 to 1.5 g / m ² on one side, an annealing furnace is used in a continuous hot dip galvanizing facility. The steel plate is subjected to annealing and hot dip galvanizing treatment at a maximum steel plate temperature of 600 ° C. or higher and 750 ° C. or lower so that internal oxidation occurs not only within the grain boundaries but also within the grains. Specifically, an oxide containing Mn is present in grains within 1 μm from the grain boundary of the underlying steel sheet in a region from immediately below the plating layer to 10 μm. The presence of oxide in the grains reduces the amount of solid solution Si and Mn in the grains near the oxide. As a result, concentration on the surface due to intragranular diffusion of Si and Mn can be suppressed.

  The structure of the surface of the underlying steel sheet immediately below the plating layer of the high-strength hot-dip galvanized steel sheet obtained by the production method of the present invention is as described above. For example, 100 μm from directly below the plating layer (plating / underlying steel sheet interface) There is no problem even if the oxide grows in a region beyond the above. Also, in the region directly below the plating layer and exceeding 10 μm from the surface of the underlying steel plate, there is no problem even if an oxide containing Mn is present in the grains of 1 μm or more from the grain boundary.

  Furthermore, in addition to the above, in the present invention, in order to improve the plating peel resistance, the steel sheet structure on which the oxide containing Mn grows is preferably a soft and rich workability ferrite phase.

Hereinafter, the present invention will be specifically described based on examples.
The hot-rolled steel sheet having the steel composition shown in Table 1 was pickled and the black scale was removed, followed by cold rolling under the conditions shown in Table 2 to obtain a cold-rolled steel sheet having a thickness of 1.0 mm.

  Next, the cold-rolled steel sheet obtained above was charged into a CGL equipped with an annealing furnace that can be controlled to an atmosphere in which the heating zone can oxidize Fe by controlling the air ratio and oxygen concentration. In CGL, the dew point in the annealing furnace is controlled to pass through the plate, and in the heating zone, Fe is oxidized to make the amount of O shown in Table 2 present, and then the steel plate temperature is increased to the maximum steel plate temperature shown in Table 2. After performing the annealing to raise, the hot dip galvanization process was performed in 460 degreeC Al containing Zn bath. The dew point and temperature were measured by sucking atmospheric gas from the center in the annealing furnace. The dew point of the annealing furnace atmosphere was −35 ° C.

Incidentally, the gas components of the atmosphere consists of N ₂ and H ₂ and inevitable impurities, for the control of the dew point of the atmosphere in advance separately N ₂ gas flows pipe humidified by heating water tank installed in an N ₂ The dew point of the atmosphere was controlled by introducing and mixing H ₂ gas in the installed and humidified N ₂ gas and introducing it into the furnace. The hydrogen concentration in the atmosphere was 10 vol%.
In addition, GA used a 0.14% Al-containing Zn bath, and GI used a 0.18% Al-containing Zn bath. The adhesion amount was adjusted to a predetermined adhesion amount (adhesion amount per side) shown in Table 2 by gas wiping, and GA was alloyed.

  The hot-dip galvanized steel sheets (GA and GI) obtained as described above were examined for appearance (plating appearance), plating peel resistance during high working, and workability. In addition, the amount of oxide (internal oxidation amount) existing in the steel plate surface layer up to 100 μm immediately below the plating layer, and the form and growth location of oxides containing Mn existing in the steel plate surface layer up to 10 μm directly below the plating layer, grains The intragranular precipitate immediately below the plating layer at a position within 1 μm from the boundary was measured. The measurement method and evaluation criteria are shown below.

<Appearance>
Appearance was judged as good appearance (symbol ◯) when there was no appearance defect such as non-plating or alloying unevenness, and when it was present, it was judged as poor appearance (symbol x).

<Plating resistance>
With regard to the resistance to plating peeling at the time of high processing, in GA, it is required to suppress plating peeling at the bent portion when bent at an acute angle exceeding 90 °. In this example, the cellophane tape (registered trademark) was pressed against the processed portion bent by 120 ° to transfer the peeled material to the cellophane tape (registered trademark), and the amount of peeled material on the cellophane tape (registered trademark) was expressed as the Zn count. Obtained by line method. At this time, the mask diameter is 30 mm, the fluorescent X-ray acceleration voltage is 50 kV, the acceleration current is 50 mA, and the measurement time is 20 seconds. In light of the following criteria, ranks 1, 2, 3, and 4 were evaluated as having good plating peel resistance (symbol ◯), and 5 having poor plating peel resistance (symbol x). ○ is a performance that has no problem with the plating peelability at the time of high processing. X is a performance not suitable for normal practical use.
Fluorescent X-ray Zn count number Rank 0 to less than 500: 1
500 or more and less than 1000: 2
1000 or more and less than −2000: 3
2000 or more and less than −3000: 4
3000 or more: 5
In GI, resistance to plating peeling during an impact test is required. A ball impact test was performed, the processed part was peeled off with tape, and the presence or absence of peeling of the plating layer was visually determined. Ball impact conditions are a ball weight of 1000 g and a drop height of 100 cm.
○: Plating layer is not peeled ×: Plating layer is peeled <Processability>
As for workability, a JIS No. 5 piece was prepared and the tensile strength (TS (MPa)) and elongation (El (%)) were measured, and those with TS × El ≧ 24000 were good, and those with TS × El <24000 were bad. did.

<Internal oxidation amount in the region of 100 μm directly under the plating layer>
The amount of internal oxidation is measured by “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 μm or more in the steel. Measure the oxygen concentration, set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally. The subsequent oxygen amount OI was used. The difference between OI and OH (= OI-OH) is calculated using the oxygen amount OI after internal oxidation of the high-strength steel plate thus obtained and the oxygen amount OH contained in the material, and further, single-sided unit area (i.e. 1 m ²⁾ value converted into the amount per (g / ^{m 2)} as an internal oxide amount.

<Growth location of oxide containing Mn present in steel plate surface layer in region up to 10 μm immediately below plating layer, intragranular precipitate immediately below plating layer at position within 1 μm from grain boundary>
After the plating layer was dissolved and removed, the cross section was observed by SEM, and the amorphous and crystalline characteristics were investigated by electron diffraction of the intragranular precipitate, and the composition was determined by EDX and EELS. When the intragranular precipitate contains Mn and O, it was determined to be an oxide containing Mn. The field of view magnification was 5000 to 20000 times, and 5 locations were investigated. When an oxide containing Mn was observed in one or more of the five places, it was determined that an oxide containing Mn was precipitated. Whether or not the growth site of internal oxidation is ferrite was examined by the cross-sectional SEM for the presence or absence of the second phase, and when the second layer was not observed, it was determined as ferrite. Also, in the region from just below the plating layer to 10 μm, the oxide containing Mn within the grain within 1 μm from the grain boundary of the underlying steel sheet is extracted by the same method as above by extracting the precipitated oxide by the extraction replica method did.

<Corrosion resistance>
A salt spray test based on JIS Z 2371 (2000) was conducted for three days on an alloyed hot-dip galvanized steel sheet with dimensions of 70 mm x 150 mm, and the corrosion product was treated with chromic acid (concentration 200 g / L, 80 ° C) for 1 minute. After washing and removing, the plating corrosion weight loss (g / m ² · day) before and after the test per one side was measured by a weight method and evaluated according to the following criteria.
○ (good): less than 20 g / m ² · day × (bad): 20 g / m ² · day or more The results obtained above are shown in Table 2 together with the production conditions.

As is apparent from Tables 2 and 3, GI and GA (invention examples) produced by the method of the present invention are high-strength steel sheets containing a large amount of oxidizable elements such as Si and Mn. Excellent workability and anti-plating resistance during high processing and good plating appearance.
On the other hand, in the comparative example, any one or more of plating appearance, workability, and resistance to plating peeling during high processing is inferior.

  The high-strength hot-dip galvanized steel sheet according to the present invention is excellent in plating appearance, corrosion resistance, workability, and anti-plating resistance during high processing, and is used as a surface-treated steel sheet for reducing the weight and strength of an automobile body. be able to. In addition to automobiles, the steel sheet can be applied in a wide range of fields such as home appliances and building materials as a surface-treated steel sheet provided with rust prevention properties.

Claims (3)

In mass%, C: 0.03 to 0.35%, Si: 0.01 to 0.50%, Mn: 3.6 to 8.0%, Al: 0.001 to 1.000%, P ≦ High strength having a galvanized layer with a coating adhesion amount of 20 to 120 g / m ^{2 on} one surface on the surface of a steel plate containing 0.10%, S ≦ 0.010%, the balance being Fe and inevitable impurities A method for producing a hot dip galvanized steel sheet,
After depositing the Fe-based oxide on the surface of the underlying steel sheet in an O amount of 0.08 to 1.5 g / m ² per side, the maximum temperature reached in the annealing furnace in the continuous hot dip galvanizing facility is 600 ° C or higher. and 750 ° C. or less, the method of producing a high strength galvanized steel sheet characterized by applying annealing and galvanizing treatment the volume fraction of H ₂ in the annealing furnace atmosphere on the steel sheet was 50% less than 1%.   The steel sheet is in mass% as a component composition, and B: 0.001 to 0.005%, Nb: 0.005 to 0.050%, Ti: 0.005 to 0.050%, Cr: 0 0.001 to 1.000%, Mo: 0.05 to 1.00%, Cu: 0.05 to 1.00%, Ni: 0.05 to 1.00%, Sn: 0.001 to 0.20 %, Sb: 0.001 to 0.20%, Ta: 0.001 to 0.10%, W: 0.001 to 0.10%, V: 0.001 to 0.10% The method for producing a high-strength hot-dip galvanized steel sheet according to claim 1, comprising at least one element.   After the hot dip galvanizing treatment, the steel plate is further heated to a temperature of 450 ° C. or higher and 600 ° C. or lower to perform alloying treatment, and the Fe content of the plating layer is in the range of 8 to 14% by mass. The manufacturing method of the high intensity | strength hot-dip galvanized steel plate of Claim 1 or 2.