HIGH-CARBON STEEL SHEET AND METHOD OF MANUFACTURING THE SAME

Information

  • Patent Application
  • 20170306434
  • Publication Number
    20170306434
  • Date Filed
    October 16, 2014
    9 years ago
  • Date Published
    October 26, 2017
    6 years ago
Abstract
A high-carbon steel sheet includes: a chemical composition represented by, in mass %, C: 0.30% to 0.70%, B: 0.0004% to 0.0035%, and others; and a structure represented by a spheroidized ratio of cementite: 80% or more; and an average diameter of cementite: 0.3 μm to 2.2 μm, wherein a coefficient of micro-friction of ferrite on a surface of the steel sheet is less than 0.5.
Description
TECHNICAL FIELD

The present invention relates to a high-carbon steel sheet with improved formability and a method of manufacturing the same.


BACKGROUND ART

A high-carbon steel sheet is used for various steel products, which are a driving system component for automobile such as a chain, a gear and a clutch, a saw, a knife, and others. When the steel products are manufactured, forming and heat treatments of a high-carbon steel sheet are performed. As the forming, punching, tensile forming, compressing, shearing, and so on are performed, and as the heat treatment, quenching, tempering, carburizing, nitriding, soft-nitriding, and so on are performed. A strength of a high-carbon steel sheet is higher than that of a mild steel sheet, and therefore a metal mold used for forming of a high-carbon steel sheet is more easily worn than a metal mold used for forming of a mild steel sheet. Further, a high-carbon steel sheet cracks more easily than a mild steel sheet during forming.


For suppressing the wearing of a metal mold, improving lubricity on a surface of a high-carbon steel sheet is effective, and for suppressing the cracking during forming, softening of a high-carbon steel sheet is effective. Thus, some techniques have been proposed aiming at an improvement in lubricity and softening (Patent Literatures 1 to 5).


However, these prior techniques cause a significant increase in cost, and therefore are not preferred.


Although a carbon steel sheet aiming at an improvement in punchability has been described in Patent Literature 6 and a high-carbon steel sheet aiming at an improvement in formability has been described in Patent Literature 7, it is not possible for them to obtain sufficient formability.


CITATION LIST
Patent Literature

Patent Literature 1: Japanese Laid-open Patent Publication No. 2010-174252


Patent literature 2: Japanese Laid-open Patent Publication No, 2009-215612


Patent Literature 3: Japanese Laid-open Patent Publication No. 2011-168842


Patent Literature 4: Japanese Laid-open Patent Publication No. 2010-255066


Patent Literature 5: Japanese Laid-open Patent Publication No, 2000-34542


Patent Literature 6: Japanese Laid-open Patent Publication No. 2000-265240


Patent Literature 7: Japanese Laid-open Patent Publication No. 10-147816


SUMMARY OF INVENTION
Technical Problem

An object of the present invention is to provide a high-carbon steel sheet capable of obtaining excellent formability while avoiding a significant increase in cost, and a method of manufacturing the same.


Solution to Problem

The present inventors conducted earnest studies repeatedly to solve the above-described problem, and consequently found out that it is important that a high-carbon steel sheet contains a specific amount of B, that a coefficient of micro-friction of ferrite on a surface is a specific one, and that form of cementite is a specific one. Further, it was also found out that, in order to manufacture such a high-carbon steel sheet, it is important to perform hot-rolling and annealing under specific conditions while assuming hot-rolling and annealing as what is called a consecutive process. Then, the inventors of the present application devised the following various aspects of the invention based on these findings.


(1)


A high-carbon steel sheet, including:


a chemical composition represented by, in mass %:


C: 0.30% to 0.70%,


Si: 0.07% to 1.00%,


Mn: 0.20% to 3.00%,


Ti: 0.010% to 0.500%,


Cr: 0.01% to 1.50%,


B: 0.0004% to 0.0035%,


F: 0.025% or less,


Al: 0.100% or less,


S: 0.0100% or less,


N: 0.010% or less,


Cu: 0.500% or less,


Nb: 0.000% to 0.500%,


Mo: 0.000% to 0.500%,


V: 0.000% to 0.500%,


W: 0.000% to 0.500%,


Ta: 0.000% to 0.500%,


Ni: 0.000% to 0.500%,


Mg: 0.000% to 0.500%,


Ca: 0.000% to 0.500%,


Y: 0.000% to 0.500%,


Zr: 0.000% to 0.500%,


La: 0.000% to 0.500%,


Ce: 0.000% to 0.500%, and


balance: Fe and impurities; and


a structure represented by:


a spheroidized ratio of cementite: 80% or more; and


an average diameter of cementite: 0.3 μm to 2.2 μm, wherein


a coefficient of micro-friction of ferrite on a surface of the steel sheet is less than 0.5.


(2)


The high-carbon steel sheet according to (1), wherein


in the chemical composition,


Nb: 0.001% to 0.500%,


Mo: 0.001% to 0.500%,


V: 0.001% to 0.500%,


W: 0.001% to 0.500%,


Ta: 0.001% to 0.500%,


Ni: 0.001% to 0.500%,


Mg: 0.001% to 0.500%,


Ca: 0.001% to 0.500%,


Y: 0.001% to 0.500%,


Zr: 0.001% to 0.500%,


La: 0.001% to 0.500%, or


Ce: 0.001% to 0.500%, or


any combination thereof is satisfied.


(3)


A method of manufacturing a high-carbon steel sheet, including:


hot-rolling of a slab so as to obtain a hot-rolled steel sheet;


pickling of the hot-rolled steel sheet; and


annealing of the hot-rolled steel sheet after the pickling,


the slab including a chemical composition represented by, in mass %:


C: 0.30% to 0.70%,


Si: 0.07% to 1.00%,


Mn: 0.20% to 3.00%,


Ti: 0.010% to 0.500%,


Cr: 0.01% to 1.50%,


B: 0.0004% to 0.0035%,


P: 0.025% or less,


Al: 0.100% or less,


S: 0.0100% or less,


N: 0.010% or less,


Cu: 0.500% or less,


Nb: 0.000% to 0.500%,


Mo: 0.000% to 0.500%,


V: 0.000% to 0.500%,


W: 0.000% to 0.500%,


Ta: 0.000% to 0.500%,


Ni: 0.000% to 0.500%,


Mg: 0.000% to 0.500%,


Ca: 0.000% to 0.500%,


Y: 0.000% to 0.500%,


Zr: 0.000% to 0.500%,


La: 0.000% to 0.500%,


Ce: 0.000% to 0.500%, and


balance: Fe and impurities, wherein


in the hot-rolling,


the slab is heated at a temperature of 1000° C. or more and less than 1150° C.,


a finish rolling temperature is 830° C. or more and 950° C. or less, and


a coiling temperature is 450° C. or more and 700° C. or less, and


the annealing comprises:


retaining the hot-rolled steel sheet at a temperature of 730° C. or more and 770° C. or less for 3 hours or more and 60 hours or less; and


then cooling the hot-rolled steel sheet down to 650° C. at a cooling rate of 1° C./hr or more and 60° C./hr or less.


(4)


The method of manufacturing the high-carbon steel sheet according to (3), wherein


in the chemical composition,


Nb: 0.001% to 0.500%,


Mo: 0.001% to 0.500%,


V: 0.001% to 0.500%,


W: 0.001% to 0.500%,


Ta: 0.001% to 0.500%,


Ni: 0.001% to 0.500%,


Mg: 0.001% to 0.500%,


Ca: 0.001% to 0.500%,


Y: 0.001% to 0.500%,


Zr: 0.001% to 0.500%,


La: 0.001% to 0.500%, or


Ce: 0.001% to 0.500%, or


any combination thereof is satisfied.


Advantageous Effects of Invention

According to the present invention, a B content, a coefficient of micro-friction of ferrite on a surface and others are appropriate, thereby making it possible to obtain excellent formability while avoiding a significant increase in cost.





BRIEF DESCRIPTION OF DRAWINGS


FIG. 1 is a chart illustrating a relationship between a coefficient of micro-friction of ferrite and a B content;



FIG. 2 is a chart illustrating a relationship between a coefficient of micro-friction of ferrite and a number of pressing until a flaw occurs;



FIG. 3A is a micrograph showing a surface of a high-carbon steel sheet before measuring a coefficient of micro-friction;



FIG. 3B is a micrograph showing the surface of the high-carbon steel sheet after measuring the coefficient of micro-friction;



FIG. 4 is a schematic diagram illustrating changes in temperature from hot-rolling to cooling;



FIG. 5A is a schematic diagram illustrating a structure at time tA;



FIG. 5B is a schematic diagram illustrating a structure at time tB;



FIG. 5C is a schematic diagram illustrating a structure at time tC;



FIG. 5D is a schematic diagram illustrating a structure at time tD;



FIG. 5E is a schematic diagram illustrating a structure at time tE;



FIG. 6A is a schematic diagram illustrating a structure when a slab heating temperature is high than 1150° C.;



FIG. 6B is a schematic diagram illustrating a structure when the slab heating temperature is lower than 1000° C.;



FIG. 6C is a schematic diagram illustrating a structure when an annealing retention temperature is lower than 730° C.;



FIG. 6D is a schematic diagram illustrating a structure when the annealing retention temperature is higher than 770° C. or an annealing retention is longer than 60 hours;



FIG. 6E is a schematic diagram illustrating a structure when the annealing retention is shorter than 3 hours;



FIG. 6F is a schematic diagram illustrating a structure when a cooling rate is less than 1° C./hr;



FIG. 6G is a schematic diagram illustrating a structure when the cooling rate is greater than 60° C./hr; and



FIG. 7 is a chart illustrating a relationship between a coefficient of micro-friction of ferrite and a B content for a part of inventive examples in a first experiment or a third experiment.





DESCRIPTION OF EMBODIMENTS

Hereinafter, there will be explained an embodiment of the present invention.


First, chemical compositions of a high-carbon steel sheet according to the embodiment of the present invention and a slab (steel ingot) used for manufacturing the same will be explained. Although details will be described later, the high-carbon steel sheet according to the embodiment of the present invention is manufactured by going through hot-rolling of the slab, annealing, and the like. Accordingly, the chemical compositions of the high-carbon steel sheet and the slab are appropriate for the above-stated processes in addition to properties of the high-carbon steel sheet. In the following description, “%” being a unit of content of each element contained in the high-carbon steel sheet and the slab used for manufacturing the same means “mass %” unless otherwise mentioned. The high-carbon steel sheet according to the embodiment and the slab used for manufacturing the same include a chemical composition represented by C: 0.30% to 0.70%, Si: 0.07% to 1.00%, Mn: 0.20% to 3.00%, Ti: 0.010% to 0.500%, Cr: 0.01% to 1.50%, B: 0.0004% to 0.0035%, P: 0.025% or less, Al: 0.100% or less, S: 0.0100% or less, N: 0.010% or less, Cu: 0.500% or less, Nb: 0.000% to 0.500%, Mo: 0.000% to 0.500%, V: 0.000% to 0.500%, W: 0.000% to 0.500%, Ta: 0.000% to 0.500%, Ni: 0.000% to 0.500%, Mg: 0.000% to 0.500%, Ca: 0.000% to 0.500%, Y: 0.000% to 0.500%, Zr: 0.000% to 0.500%, La: 0.000% to 0.500%, Ce: 0.000% to 0.500%, and balance: Fe and impurities. As the impurities, ones contained in raw materials such as ore and scrap, and ones contained during a manufacturing process are exemplified. For example, when scrap is used as a raw material, Sn, Sb or As or any combination thereof may mix in by 0.003% or more. If the content is 0.03% or less, none of them hinder the effect of the embodiment, and thus may be tolerated as impurities. Further, O may be tolerated as an impurity up to 0.0025%. O forms oxide, and when oxides aggregate and become coarse, sufficient formability is not obtained. Therefore, the O content is the lower the better. However, it is technically difficult to decrease the O content to less than 0.0001%.


(C: 0.30% to 0.70%)


C bonds to Fe to form cementite having a small friction coefficient, and thus is an important element when securing macro-lubricity of the high-carbon steel sheet. When the C content is less than 0.30%, the amount of cementite is insufficient, resulting in that sufficient lubricity cannot be obtained and adhesion to a metal mold occurs during forming. Thus, the C content is 0.30% or more, and preferably 0.35% or more. When the C content is greater than 0.70%, the amount of cementite is excessive, resulting in that a crack originating from the cementite occurs easily during forming. Thus, the C content is 0.70% or less, and preferably 0.65% or less.


(Si: 0.07% to 1.00%)


Si operates as a deoxidizes, and is effective for suppressing excessive coarsening of cementite during annealing. When the Si content is less than 0.07%, the effect by the above-described operation cannot be obtained sufficiently. Thus, the Si content is 0.07% or more, and preferably 0.10% or more. When the Si content is greater than 1.00%, the ductility of ferrite is low and a crack originating from transgranular fracture of ferrite occurs easily during forming. Thus, the Si content is 1.00% or less, and preferably 0.80% or less.


(Mn: 0.20% to 3.00%)


Mn is important for controlling pearlite transformation. When the Mn content is less than 0.20%, the effect by the above-described operation cannot be obtained sufficiently. That is, when the Mn content is less than 0.20%, pearlite transformation occurs in cooling after dual-phase annealing and a spheroidized ratio of cementite becomes insufficient. Thus, the Mn content is 0.20% or more, and preferably 0.25% or more. When the Mn content is greater than 3.00%, the ductility of ferrite is low and a crack originating from transgranular fracture of ferrite occurs easily during forming. Thus, the Mn content is 3.00% or less, and preferably 2.00% or less.


(Ti: 0.010% to 0.500%)


Ti forms a nitride in molten steel, and effective for preventing formation of BN. When the Ti content is less than 0.010%, the effect by the above-described operation cannot be obtained sufficiently. Thus, the Ti content is 0.010% or more, and preferably 0.040% or more. When the Ti content is greater than 0.500%, a crack originating from a coarse oxide of Ti occurs easily during forming. This is because during continuous casting, coarse oxides of Ti are formed to get involved inside the slab. Thus, the Ti content is 0.500% or less, and preferably 0.450% or less.


(Cr: 0.01% to 1.50%)


Cr has a high affinity with N, effective for suppressing formation of BN, and effective also for controlling pearlite transformation. When the Cr content is less than 0.01%, the effect by the above-described operation cannot be obtained sufficiently. Thus, the Cr content is 0.01% or more, and preferably 0.05% or more. When the Cr content is greater than 1.50%, spheroidizing of cementite during annealing is hindered and coarsening of cementite is suppressed drastically. Thus, the Cr content is 1.50% or less, and preferably 0.90% or less.


(B: 0.0004% to 0.0035%)


B lowers the coefficient of micro-friction of ferrite on the surface of the high-carbon steel sheet. B segregates to and concentrates at an interface between ferrite and cementite during later-described annealing and suppresses peeling at the interface during forming, and B is also effective for preventing a crack. When the B content is less than 0.0004%, the effect by the above-described operation cannot be obtained sufficiently. Thus, the B content is 0.0004% or more, and preferably 0.0008% or more. When the B content is greater than 0.0035%, a crack originating from boride such as carbide of Fe and B occurs easily during forming. Thus, the B content is 0.0035% or less, and preferably 0.0030% or less.



FIG. 1 is a chart illustrating a relationship between a coefficient of micro-friction of ferrite and a B content. As illustrated in FIG. 1, when the B content is 0.0004% or more, the coefficient of micro-friction of ferrite is significantly low as compared to the case when it is less than 0.0004%. It may be inferred that the reason why wearing of a metal mold can be suppressed as a coefficient of micro-friction of ferrite is lower is because a hard film of B is formed on a surface of a high-carbon steel sheet, as will be described later. Further, it may be inferred that the operation that B segregated to and concentrated at an interface between ferrite and cementite improves strength of the interface, suppresses cracking of a high-carbon steel sheet, and suppresses wearing of a metal mold caused by cracking is also a reason for the above.


(P: 0.025% or less)


P is not an essential element and is contained as an impurity in the steel sheet, for example. P strongly segregates to the interface between ferrite and cementite, and thereby the segregation of B to the interface is hindered and peeling at the interface is caused. Therefore, the P content is the smaller the better. When the P content is greater than 0.025%, adverse effects are particularly prominent. Thus, the P content is 0.025% or less. Decreasing the P content takes refining cost, and it requires a considerable refining cost to decrease the P content to less than 0.0001%. Thus, the P content may be 0.0001% or more.


(Al: 0.100% or less)


Al operates as a deoxidizer in steelmaking and is effective for fixing N, but is not an essential element of the high-carbon steel sheet and is contained as an impurity in the steel sheet, for example. When the Al content is greater than 0.100%, the ductility of ferrite is low and a crack originating from transgranular fracture of ferrite occurs easily during forming, and strength is excessive to cause an increase in forming load. Thus, the Al content is set to 0.100% or less. When the Al content of the high-carbon steel sheet is less than 0.001%, fixation of N sometimes may be insufficient. Thus, the Al content may be 0.001% or more.


(S: 0.0100% or less)


S is not an essential element and is contained as an impurity in the steel sheet, for example. S forms coarse non-metal inclusions such as MnS to impair formability. Therefore, the S content is the smaller the better. When the S content is greater than 0.0100%, adverse effects are particularly prominent. Thus, the S content is 0.0100% or less. Decreasing the S content takes refining cost, and it requires a considerable refining cost to decrease the S content to less than 0.0001%. Thus, the S content may be 0.0001% or more.


(N: 0.010% or less)


N is not an essential element and is contained as an impurity in the steel sheet, for example. N lowers an amount of solid-solution B due to formation of BN so as to cause adhesion to the metal mold, cracking during forming, and the like. Therefore, the N content is the smaller the better. When the N content is greater than 0.010%, adverse effects are particularly prominent. Thus, the N content is set to 0.010% or less. Decreasing the N content takes refining cost, and it requires a considerable refining cost to decrease the N content to less than 0.001%. Thus, the N content may be 0.001% or more.


(Cu: 0.000% to 0.500%)


Cu is not an essential element and is mixed from scrap or the like to be contained as an impurity in the steel sheet, for example. Cu causes an increase in strength and brittleness in hot working. Therefore, the Cu content is the smaller the better. When the Cu content is greater than 0.500%, adverse effects are particularly prominent. Thus, the Cu content is 0.500% or less. Decreasing the Cu content takes refining cost, and it requires a considerable refining cost to decrease the Cu content to less than 0.001%. Thus, the Cu content may be 0.001% or more.


Nb, Mo, V, W, Ta, Ni, Mg, Ca, Y, Zr, La, and Ce are not essential elements, and are optional elements that may be appropriately contained in the high-carbon steel sheet and the slab up to a specific amount.


(Nb: 0.000% to 0.500%)


Nb forms a nitride and is effective for suppressing formation of BN. Thus, Nb may be contained. However, when the Nb content is greater than 0.500%, the ductility of ferrite is low to make it impossible to obtain sufficient formability. Thus, the Nb content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Nb content is preferably 0.001% or more.


(Mo: 0.000% to 0.500%)


Mo is effective for improving hardenability. Thus, Mo may be contained. However, when the Mo content is greater than 0.500%, the ductility of ferrite is low to make it impossible to obtain sufficient formability. Thus, the Mo content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Mo content is preferably 0.001% or more.


(V: 0.000% to 0.500%)


V forms a nitride and is effective for suppressing formation of BN similarly to Nb. Thus, V may be contained. However, when the V content is greater than 0.500%, the ductility of ferrite is low to make it impossible to obtain sufficient formability. Thus, the V content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the V content is preferably 0.001% or more.


(W: 0.000% to 0.500%)


W is effective for improving hardenability similarly to Mo. Thus, W may be contained. However, when the N content is greater than 0.500%, the ductility of ferrite is low to make it impossible to obtain sufficient formability. Thus, the W content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the W content is preferably 0.001% or more.


(Ta: 0.000% to 0.500%)


Ta forms a nitride and is effective for suppressing formation of BN similarly to Nb and V. Thus, Ta may be contained. However, when the Ta content is greater than 0.500%, the ductility of ferrite is low to make it impossible to obtain sufficient formability. Thus, the Ta content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Ta content is preferably 0.001% or more.


(Ni: 0.000% to 0.500%)


Ni is effective for improving toughness and improving hardenability. Thus, Ni may be contained. However, when the Ni content is greater than 0.500%, the coefficient of micro-friction of ferrite is high to cause adhesion to the metal mold easily. Thus, the Ni content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Ni content is preferably 0.001% or more.


(Mg: 0.000% to 0.500%)


Mg is effective for controlling the form of sulfide. Thus, Mg may be contained. However, Mg forms oxide easily, and when the Mq content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the Mg content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Mg content is preferably 0.001% or more.


(Ca: 0.000% to 0.500%)


Ca is effective for controlling the form of sulfide similarly to Mg. Thus, Ca may be contained. However, Ca forms oxide easily, and when the Ca content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the Ca content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Ca content is preferably 0.001% or more.


(Y: 0.000% to 0.500%)


Y is effective for controlling the form of sulfide similarly to Mg and Ca. Thus, Y may be contained. However, Y forms oxide easily, and when the Y content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the Y content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Y content is preferably 0.001% or more.


(Zr: 0.000% to 0.500%)


Zr is effective for controlling the form of sulfide similarly to Mg, Ca, and Y. Thus, Zr may be contained. However, Zn forms oxide easily, and when the Zr content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the Zr content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Zr content is preferably 0.001% or more.


(La: 0.000% to 0.500%)


La is effective for controlling the form of sulfide similarly to Mg, Ca, Y, and Zr. Thus, La may be contained. However, La forms oxide easily, and when the La content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the La content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the La content is preferably 0.001% or more.


(Ce: 0.000% to 0.500%)


Ce is effective for controlling the form of sulfide similarly to Mg, Ca, Y, Zr, and La. Thus, Ce may be contained. However, Ce forms oxide easily, and when the Ce content is greater than 0.500%, sufficient formability cannot be obtained due to a crack originating from the oxide. Thus, the Ce content is 0.500% or less. In order to securely obtain the effect by the above-described operation, the Ce content is preferably 0.001% or more.


Thus, Nb, Mo, V, W, Ta, Ni, Mg, Ca, Y, Zr, La and Ce are optional elements, and it is preferred that “Nb: 0.001% to 0.500%,” “Mo: 0.001% to 0.500%,” “V: 0.001% to 0.500%,” “W: 0.001% to 0.500%,” “Ta: 0.001% to 0.500%,” “Ni: 0.001% to 0.500%,” “Mg: 0.001% to 0.500%,” “Ca: 0.001% to 0.500%,” “Y: 0.001% to 0.500%,” “Zr: 0.001% to 0.500%,” “La: 0.001% to 0.500%,” or “Ce: 0.001% to 0.500%,” or any combination thereof be satisfied.


Next, the coefficient of micro-friction of ferrite on the surface of the high-carbon steel sheet according to the embodiment is explained. The coefficient of micro-friction of ferrite on the surface of the high-carbon steel sheet according to the embodiment is less than 0.5.


(Coefficient of Micro-Friction of Ferrite on the Surface: Less than 0.5)


The coefficient of micro-friction of ferrite on the surface closely relates to adhesion of the high-carbon steel sheet to the metal mold during forming. When the coefficient of micro-friction of ferrite is 0.5 or more, micro-adhesion occurs between the high-carbon steel sheet and the metal mold during forming using the metal mold. As a result, when forming such as punching is performed with several thousands to several tens of thousands of shots by using the metal mold, adhesive matters are accumulated on the metal mold during the forming, and a flaw occurs on either the metal mold or the high-carbon steel sheet or on the both and formability deteriorates. Thus, the coefficient of micro-friction of ferrite is less than 0.5. From the viewpoint of formability, the coefficient of micro-friction is the lower the better. The coefficient of micro-friction often tends to be 0.35 or more, though it depends on a method of manufacturing the high-carbon steel sheet and others.



FIG. 2 is a chart illustrating a relationship between a coefficient of micro-friction of ferrite and a number of pressing (shots) until a flaw occurs on a metal mold or a high-carbon steel sheet in punch forming of high-carbon steel sheets. As illustrated in FIG. 2, when the coefficient of micro-friction is less than 0.5, the number of pressing until a flaw occurs is significantly high as compared to the case when it is 0.5 or more.


A coefficient of micro-friction may be measured using a nanoindenter. That is, a kinetic friction force F to occur when a diamond indenter loads a normal load P of 10 μN onto a surface of a high-carbon steel sheet and is moved horizontally is obtained. A moving speed then is 1 μm/second, for example. A coefficient of micro-friction μ (kinetic friction coefficient) is calculated by Expression (1) below. “TI-900 TriboIndenter” made by Omicron, Inc. may be used as a nanoindenter, for example.





F=μP  Expression(1)



FIG. 3A is a micrograph showing a surface of a high-carbon steel sheet before measuring a coefficient of micro-friction, and FIG. 3B is a micrograph showing the surface of the high-carbon steel sheet after measuring the coefficient of micro-friction. FIG. 3A and FIG. 3B each show an example of a 10 μm×10 μm visual field. As shown in FIG. 3A and FIG. 3B, ferrite 31 and cementite 32 exist in the visual field example. Further, as shown in FIG. 3B, measurement flaws 33 caused by horizontal movement of the diamond indenter exist after the measurement. The coefficient of micro-friction of cementite was 0.4 or less.


Next, a structure of the high-carbon steel sheet according to the embodiment is explained. The high-carbon steel sheet according to the embodiment includes a structure represented by a spheroidized ratio of cementite: 80% or more and an average diameter of cementite: 0.3 μm to 2.2 μm.


(Spheroidized Ratio of Cementite: 80% or More)


Stress concentration sometimes originates from cementite during forming, and stress is likely to concentrate locally in acicular cementite particularly. When the spheroidized ratio of cementite is less than 80%, acicular cementite, in which stress is likely to concentrate, is contained in large amounts, and thus stress concentration occurs easily and peeling occurs at an interface between ferrite and cementite, resulting in that sufficient formability cannot be obtained. Thus, the spheroidized ratio of cementite is 80% or more, and preferably 85% or more. From the viewpoint of formability, the spheroidized ratio of cementite is preferred to be as higher as possible, and may be 100%. However, when the spheroidized ratio of cementite is attempted to become 100%, productivity could decrease, and the spheroidized ratio of cementite is preferably 80% or more and less than 100% from the viewpoint of productivity.


(Average Diameter of Cementite: 0.3 μm to 2.2 μm)


The average diameter of cementite closely relates to the degree of the stress concentration to cementite. When the average diameter of cementite is less than 0.3 μm, an Orowan loop is formed by dislocation occurred during forming with respect to cementite, and thereby a dislocation density in the vicinity of cementite increases and voids occur. Thus, the average diameter of cementite is 0.3 μm or more, and preferably 0.5 μm or more. When the average diameter of cementite is greater than 2.2 μm, dislocations occurred during forming are accumulated in large amounts, local stress concentration is generated and a crack occurs. Thus, the average diameter of cementite is 2.2 μm or less, and preferably 2.0 μm or less.


The spheroidized ratio and the average diameter of cementite may be measured by structure observation using a scanning electron microscope. In preparing of a sample for structure observation, an observation surface is mirror finished by wet polishing with an emery paper and polishing with diamond abrasive grains having a size of 1 μm, then the observation surface is etched with an etching solution of 3 vol % of nitric acid and 97 vol % of alcohol. An observation magnification is between 3000 times to 10000 times, for example, 10000 times, 16 visual fields where 500 or more grains of cementite exist on the observation surface are selected, and structure images of them are taken. Then, an area of each cementite in the structure image is measured by using image processing software. “Win ROOF” made by MITANI Corporation may be used as an image processing software, for example. Any cementite grain having an area of 0.01 μm2 or less is excluded from the target of evaluation in order to suppress an influence of measurement error by noise in the measuring. Then, the average area of cementite as an evaluation target is obtained, and the diameter of a circle with which this average area can be obtained is obtained, thereby taking this diameter as the average diameter of cementite. The average area of cementite is a value obtained by dividing the total area of cementite as the evaluation target by the number of grains of cementite in question. Further, any cementite having a ratio of major axis length to minor axis length of 3 or more is assumed as an acicular cementite, any cementite having the ratio of less than 3 is assumed as a spherical cementite grain, and a value obtained by dividing the number of spherical cementite by the number of all cementite is taken as the spheroidized ratio of cementite.


Next, a method of manufacturing the high-carbon steel sheet according to the embodiment is explained. The manufacturing method includes hot-rolling of a slab including the above chemical composition so as to obtain a hot-rolled steel sheet, pickling of the hot-rolled steel sheet, and thereafter annealing of the hot-rolled steel sheet. In the hot-rolling, the slab is heated at a temperature of 1000° C. or more and less than 1150° C., a finish rolling temperature is 830° C. or more and 950° C. or less, and a coiling temperature is 450° C. or more and 700° C. or less. In the annealing, the hot-rolled steel sheet is retained at a temperature of 730° C. or more and 770° C. or less for 3 hours or more and 60 hours or less, and then, the hot-rolled steel sheet is cooled down to 650° C. at a cooling rate of 1° C./hr or more and 60° C./hr or less. An atmosphere of the annealing may be one containing hydrogen by 75 vol % or more at a temperature higher than 400° C., for example, but is not limited to that.


Here, an outline of changes in the steel sheet from the hot-rolling to the cooling is explained. FIG. 4 is a schematic diagram illustrating changes in temperature. FIG. 5A to FIG. 55 are schematic diagrams illustrating changes in structure.


In an example illustrated in FIG. 4, hot-rolling S1 includes slab heating S11, finish rolling S12, and coiling S13, and annealing S3 includes high-temperature retention S31 and cooling S32. Pickling S2 is performed between the hot-rolling S1 and the annealing S3, and after cooling S4 is performed the annealing S3.


At a time tA after completion of the slab heating S11, B atoms 13 segregate to an interface between austenite 12 and austenite 12, as illustrated in FIG. 5A. At a time tB after completion of the high-temperature retention S31, the structure of the steel sheet contains ferrite 11 and the austenite 12, as illustrated in FIG. 5B. Further, the B atoms 13 segregate to an interface between the ferrite 11 and the austenite 12. Some of the B atoms 13 are present also on a surface 15 of the steel sheet, and the B atoms 13 present on the surface of the steel sheet are bonded to each other by covalent bonding 14. Although not illustrated in FIG. 5B, cementite is also contained in the structure of the steel sheet and some of the B atoms 13 segregate also to an interface between the ferrite 11 and the cementite. At a time tC in a middle of the cooling S32, the ratio of the ferrite 11 increases and the ratio of the austenite 12 decreases as compared to the structure illustrated in FIG. 5B, as illustrated in FIG. 5C, and the interface between these two phases moves due to the increasing and decreasing or the ratios. Also, the B atoms 13 present on the surface of the steel sheet increase with the movement of the interface. Further, at a time tD when the cooling S32 has advanced, the ratio of the ferrite 11 increases, the ratio of the austenite 12 decreases, and the B atoms 13 present on the surface of the steel sheet increase as compared to the structure illustrated in FIG. 5C, as illustrated in FIG. 5D. Then, at a time tE, when the temperature of the steel sheet has reached 650° C., the austenite 12 disappears and the surface 15 of the steel sheet is covered with many of the B atoms 13, as illustrated in FIG. 5E. Since the B atoms 13 are bonded to each other by the covalent bonding 14, they are crystallized. The structure illustrated in FIG. 5E does not change also during the cooling S4, and is maintained even when the temperature of the steel sheet has reached room temperature, for example, a temperature of less than 600° C.


According to the manufacturing method, the surface 15 of the steel sheet is covered with many of the B atoms 13 bonded to each other by the covalent bonding 14, and thereby the coefficient of micro-friction of ferrite on the surface 15 can be less than 0.5.


(Slab Heating Temperature: 1000° C. or More and Less than 1150° C.)


When the slab heating temperature is higher than 1150° C., oxygen easily diffuses into the inside of the slab from the surface of the slab to bond to B in the slab. That is, as illustrated in FIG. 6A, the B atoms 13 are consumed due to bonding to O atoms 16. Therefore, even though a process thereafter is performed appropriately, it is not possible to obtain a good surface covered with crystals of B, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Thus, the slab heating temperature is 1150° C. or less, and preferably 1140° C. or less. When the slab heating temperature is lower than 1000° C., micro-segregation and/or macro-segregation formed during casting cannot be eliminated, and as illustrated in FIG. 6B, solidification segregations of the B atoms 13 remain. The solidification segregations of the B atoms 13 cannot be eliminated even though a process thereafter is performed appropriately, and therefore, it is not possible to obtain a good surface covered with crystals of B, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Further, when the slab heating temperature is lower than 1000° C., regions where Cr atoms and/or Mn atoms segregate and concentrate also remain in the high-carbon steel sheet. Therefore, even though a process thereafter is performed appropriately, cracks occur from the regions during forming, thus making it impossible to obtain good formability. Thus, the slab heating temperature is 1000° C. or more, and preferably 1030° C. or more.


(Finish Rolling Temperature: 830° C. or More and 950° C. or Less)


When the finish rolling temperature is higher than 950° C., coarse scales are generated until completion of coiling on a run out table (ROT), for example. The coarse scales can be removed by pickling, but traces of large irregularities are left, resulting in that adhesion to the metal mold sometimes occurs during forming due to the traces. Further, when coarse scales are generated, irregular flaw is caused on the surface of the steel sheet in the coiling, resulting in that due to the flaw, adhesion to the metal mold sometimes occurs during forming. Thus, the finish rolling temperature is 950° C. or less, and preferably 940° C. or less. When the finish rolling temperature is lower than 830° C., adhesiveness of scales generated until completion of coiling to the steel sheet is extremely high, thus making it difficult to remove the scales by pickling. The scales may be removed by performing strong pickling, but the strong pickling makes the surface of the steel sheet rough, resulting in that adhesion to the metal mold sometimes occurs during forming. Further, when the finish rolling temperature is lower than 830° C., recrystallization of austenite is not completed by the coiling, so that anisotropy of the hot-rolled steel sheet increases. The anisotropy of the hot-rolled steel sheet is carried over even after annealing, and thus sufficient formability cannot be obtained. Thus, the finish rolling temperature is 830° C. or more, and preferably 840° C. or more.


(Coiling Temperature: 450° C. or More and 700° C. or Less)


When the coiling temperature is higher than 700° C., coarse lamellar pearlite is formed in the hot-rolled steel sheet to hinder spheroidizing of cementite during annealing, resulting in that the spheroidized ratio of 80% or more cannot be obtained. Thus, the coiling temperature is 700° C. or less. Further, when the coiling temperature is higher than 570° C., coarse scales are generated until completion of coiling. Therefore, adhesion to the metal mold sometimes occurs during forming for a reason similar to the case where the finish rolling temperature is higher than 950° C. Thus, the coiling temperature is preferably 570° C. or less, and further preferably 550° C. or less. When the coiling temperature is lower than 450° C., adhesiveness of scales generated until completion of coiling to the steel sheet is extremely high, thus making it difficult to remove the scales by pickling. The scales may be removed by performing strong pickling, but the strong pickling makes the surface of the steel sheet rough, resulting in that adhesion to the metal mold sometimes occurs during forming. Further, when the coiling temperature is lower than 450° C., the hot-rolled steel sheet becomes brittle and the hot-rolled steel sheet may crack when a coil is uncoiled in pickling, resulting in that a sufficient yield cannot be obtained. Thus, the coiling temperature is 450° C. or more, and preferably 460° C. or more.


A rough-rolled bar may be heated near an inlet of a finishing mill in order to ensure qualities in a longitudinal direction and a width direction of a hot-rolled coil obtained by coiling (to reduce variation of quality or the like). An apparatus to be used for the heating and a method of the heating are not limited in particular, but heating by high-frequency induction heating is desirably performed. A preferred temperature range of the heated rough-rolled bar is between 850° C. and 1100° C. Temperatures less than 850° C. are close to a transformation temperature from austenite to ferrite, and therefore, when the temperature of the heated rough bar is lower than 850° C., heat generation and heat absorption due to transformation and reverse transformation sometimes occur, resulting in that temperature controlling is unstable and it is difficult to uniformize a temperatures in the longitudinal direction and the width direction of the hot-rolled coil. Therefore, if the rough-rolled bar is heated, the heating temperature is preferably 850° C. or more. Increasing the temperature of the rough-rolled bar to temperature higher than 1100° C. takes excessive time, and the productivity decreases. Therefore, if rough-rolled bar is heated, the heating temperature is preferably 1100° C. or less.


(Annealing Retention Temperature: 730° C. or More and 770° C. or Less)


When the annealing retention temperature is lower than 730° C., the austenite 12 is not formed sufficiently, and as illustrated in FIG. 6C, although a large number of interfaces between the ferrite 11 and the ferrite 11 exist, sites where the B atom 13 segregates are insufficient. Therefore, even though a process thereafter is performed appropriately, a good surface covered with crystals of B cannot be obtained, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Further, when the annealing retention temperature is lower than 730° C., segregation of the B atom 13 to the interface between the ferrite 11 and cementite does not occur easily, and therefore, segregating the B atoms 13 sufficiently takes an extremely long time, which is about 100 hours, and the productivity decreases. Thus, the annealing retention temperature is 730° C. or more, and preferably 735° C. or more. When the annealing retention temperature is higher than 770° C., as illustrated in FIG. 6D, the B atoms 13 concentrate and coarse crystals of B are formed in the vicinity of the triple point of the ferrite 11, the austenite 12, and the surface of the steel sheet. When coarse crystals of B are formed, even though a process thereafter is performed appropriately, the thickness of a film of the crystals of B varies greatly, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Further, when the annealing retention temperature is higher than 770° C., thermal expansion of the hot-rolled steel sheet coiled in a coil shape is large, and the hot-rolled steel sheet itself sometimes rubs together during annealing to cause abrasions on the surface. The appearance of the surface is impaired and the yield is decreased by the abrasions. Thus, the annealing retention temperature is 770° C. or less, and preferably 765° C. or less.


(Annealing Retention Time: 3 Hours or More and 60 Hours or Less)


When the annealing retention time is less than 3 hours, as illustrated in FIG. 6E, the B atoms 13 do not sufficiently segregate to the interface between the ferrite 11 and the austenite 12, and therefore, even though a process thereafter is performed appropriately, a good surface covered with crystals of B cannot be obtained, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Further, when the annealing retention time is less than 3 hours, cementite does not become coarse sufficiently, resulting in that the average diameter of cementite cannot be 0.3 μm or more. Thus, the annealing retention time is 3 hours or more, and preferably 5 hours or more. When the annealing retention time is greater than 60 hours, the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5 for a reason similar to the case where the annealing retention temperature is higher than 770° C. Further, when the annealing retention time is greater than 60 hours, cementite becomes coarse excessively, resulting in that the average diameter of cementite cannot be 2.2 μm or less. Thus, the annealing retention time is 60 hours or less, and preferably 40 hours or less.


(Cooling Rate Down to 650° C.: 1° C./Hr or More and 60° C./Hr or Less)


When the cooling rate down to 650° C. is less than 1° C./hr, as illustrated in FIG. 6F, crystals of B are formed excessively during cooling and the crystals of B form a projection on the surface of the high-carbon steel sheet. Once a projection is formed, the thickness of the film of the crystals of B varies greatly, resulting in that adhesion to the metal mold occurs during forming and a flaw occurs on the metal mold. Further, when the cooling rate down to 650° C. is less than 1° C./hr, sufficient productivity cannot be obtained. Thus, the cooling rate down to 650° C. is 1° C./hr or more, and preferably 2° C./hr or more. When the cooling rate down to 650° C. is greater than 60° C./hr, a decrease rate of the austenite 12 is excessive, and as illustrated in FIG. 6G, the sufficient covalent bonding 14 cannot be caused between the B atoms 13, resulting in that the coefficient of micro-friction of ferrite on the surface cannot be less than 0.5. Further, when the cooling rate down to 650° C. is greater than 60° C./hr, pearlite is formed from the austenite 12 during cooling to hinder spheroidizing of cementite, resulting in that the spheroidized ratio of 80% or more cannot be obtained. Thus, the cooling rate down to 650° C. is 60° C./hr or less, and 50° C./or less.


According to the embodiment, excellent lubricity can be obtained, and therefore it is possible to suppress adhesion of the high-carbon steel sheet to the metal mold and suppress wearing of the metal mold. Further, according to the embodiment, it is also possible to suppress cracking during forming.


It should be noted that all of the above-described embodiments merely illustrate concrete examples of implementing the present invention, and the technical scope of the present invention is not to be construed in a restrictive manner by these embodiments. That is, the present invention may be implemented in various forms without departing from the technical spirit or main features thereof.


EXAMPLE

Next, examples of the present invention will be described. Conditions in the examples are condition examples employed for confirming feasibility and effect of the present invention, and the present invention is not limited to these condition examples. The present invention can employ various conditions as long as the object of the present invention is achieved without departing from the spirit of the invention.


First Experiment

In a first experiment, hot-rolling of a slab (Steel type A to Y, BK) including a chemical composition listed in Table 1 was performed, thereby obtaining a hot-rolled steel sheet having a thickness of 4 mm. In the hot-rolling, the slab heating temperature was 1130° C., the time thereof was 1 hour, the finish rolling temperature was 850° C., and the coiling temperature was 520° C. Then, cooling was performed down to a temperature of less than 60° C., and pickling using sulfuric acid was performed. Thereafter, annealing of the hot-rolled steel sheet was performed to then obtain a hot-rolled annealed steel sheet. In the annealing, the hot-rolled steel sheet was retained for 15 hours at 750° C., and then was cooled down to 650° C. at a cooling rate of 30° C./hr. Subsequently, cooling was performed down to a temperature of less than 60° C. In this manner, various high-carbon steel sheets were manufactured. Blank fields in Table 1 indicate that the content of the element is less than a detection limit, and the balance is Fe and impurities. For example, the Cr content of Steel type BK may be regarded as 0.00%. An underline in Table 1 indicates that the numeric value is out of the range of the present invention.










TABLE 1







STEEL
CHEMICAL COMPONENT (MASS %)




















TYPE
C
Si
Mn
P
S
Al
N
Ti
Cr
B
Nb
Mo
V





A
0.32
0.78
1.21
0.023
0.0062
0.088
0.003
0.203
0.11
0.0022


B
0.38
0.41
0.61
0.014
0.0064
0.035
0.002
0.332
0.39
0.0029


C
0.41
0.32
1.40
0.013
0.0051
0.085
0.004
0.157
0.77
0.0018


D
0.47
0.08
0.27
0.015
0.0085
0.072
0.006
0.282
1.22
0.0015


E
0.53
0.19
1.67
0.010
0.0039
0.060
0.003
0.348
0.54
0.0011


F
0.61
0.74
1.86
0.017
0.0097
0.048
0.006
0.046
1.32
0.0023


G
0.64
0.97
0.99
0.002
0.0056
0.082
0.003
0.499
0.05
0.0005


H
0.64
0.47
2.92
0.021
0.0003
0.011
0.008
0.163
0.47
0.0009


I
0.67
0.60
1.48
0.024
0.0041
0.053
0.006
0.421
0.88
0.0008


J

0.29

0.16
2.46
0.005
0.0006
0.027
0.002
0.042
0.88
0.0011


K
0.31
0.17
2.34
0.006
0.0056
0.049

0.011

0.061
0.67
0.0016


L
0.32
0.55
1.15
0.002
0.0017

0.110

0.005
0.194
0.29
0.0019


M
0.32
0.27
0.42
0.022
0.0094
0.006
0.005
0.057
1.46

0.0036



N
0.36
0.60

0.18

0.015
0.0045
0.008
0.009
0.138
0.57
0.0011


O
0.39
0.61
2.70

0.026

0.0003
0.024
0.002
0.056
1.20
0.0033


P
0.40

1.05

1.97
0.001
0.0095
0.070
0.006
0.445
0.36
0.0024


Q
0.40
0.67
0.58
0.006
0.0012
0.033
0.002
0.381
0.21

0.0001



R
0.41
0.21
1.74
0.006
0.0092
0.098
0.002
0.435
1.00

0.0002



S
0.49

0.06

0.53
0.018
0.0053
0.086
0.002
0.321
0.91
0.0014


T
0.53
0.35
1.72
0.003

0.0122

0.055
0.008
0.201
0.42
0.0034


U
0.65
0.78

3.10

0.005
0.0052
0.011
0.004
0.332
0.02
0.0013


V
0.70
0.58
0.60
0.019
0.0048
0.046
0.002
0.136

1.55

0.0029


W

0.78

0.91
2.01
0.005
0.0046
0.076
0.009
0.487
1.37
0.0028


X
0.42
0.24
0.58
0.011
0.0062
0.024
0.005

0.006

0.88
0.0022


Y
0.47
0.99
0.51
0.019
0.0093
0.091
0.009

0.519

1.06
0.0030


BK
0.37
0.38
1.24
0.018
0.0088
0.063
0.007
0.121

0.0022
















STEEL
CHEMICAL COMPONENT (MASS %)
Ac1
Ac3























TYPE
Cu
W
Ta
Ni
Mg
Ca
Y
Zr
La
Ce
(° C.)
(° C.)
REMARKS







A










732
850
INVENTIVE
















EXAMPLE



B










737
810
INVENTIVE
















EXAMPLE



C










731
811
INVENTIVE
















EXAMPLE



D










743
781
INVENTIVE
















EXAMPLE



E










714
758
INVENTIVE
















EXAMPLE



F










748
788
INVENTIVE
















EXAMPLE



G










735
766
INVENTIVE
















EXAMPLE



H










715
758
INVENTIVE
















EXAMPLE



I










740
755
INVENTIVE
















EXAMPLE



J










709
818
COMPARATIVE
















EXAMPLE



K










711
819
COMPARATIVE
















EXAMPLE



L










731
840
COMPARATIVE
















EXAMPLE



M










747
828
COMPARATIVE
















EXAMPLE



N










750
838
COMPARATIVE
















EXAMPLE



O










728
814
COMPARATIVE
















EXAMPLE



P










740
823
COMPARATIVE
















EXAMPLE



Q










740
814
COMPARATIVE
















EXAMPLE



R










725
782
COMPARATIVE
















EXAMPLE



S










730
764
COMPARATIVE
















EXAMPLE



T










722
778
COMPARATIVE
















EXAMPLE



U










709
756
COMPARATIVE
















EXAMPLE



V










758
775
COMPARATIVE
















EXAMPLE



W










747
751
COMPARATIVE
















EXAMPLE



X










738
808
COMPARATIVE
















EXAMPLE



Y










760
804
COMPARATIVE
















EXAMPLE



BK










721
816
COMPARATIVE
















EXAMPLE










Then, the coefficient of micro-friction of ferrite, and the spheroidized ratio and the average diameter of cementite of each of the high-carbon steel sheets were measured. A friction coefficient of cementite was also measured in measuring the coefficient of micro-friction of ferrite. Results of them are listed in Table 2. An underline in Table 2 indicates that the item is out of the range of the present invention.


Further, evaluation of adhesion suppressive performance and evaluation of crack sensitivity of each of the high-carbon steel sheets were performed as formability evaluation. In the evaluation of adhesion suppressive performance, a draw bead test was performed. That is, an indentation bead with a tip having a 20 mm radius R was pressed against the high-carbon steel sheet with a load of 10 kN and was pulled out. Then, presence or absence of adhesive matter on the tip of the indentation bead was observed, and one with presence of adhesive matter was evaluated as X and one with no presence was evaluated as ◯. The presence of adhesive matter in this test indicates that in press forming with several thousands to several tens of thousands of shots, an adhesive matter occurs early on the metal mold to deteriorate formability. In the evaluation of crack sensitivity, a compression test was performed. That is, a cylindrical test piece having a 10 mm diameter and a 4 mm height was cut out from the high-carbon steel sheet so that a height direction of the test piece was parallel to a sheet thickness direction, and the test piece was compressed to 1 mm in height. Then, an appearance observation and a sectional structure observation were performed, and then one in which cracking appeared in the appearance during compression or after compression and one in which a crack of 1 mm or more was present in the sectional structure observation were evaluated as X, and one other than the above was evaluated as ◯. Results of them are also listed in Table 2.

















TABLE 2







COEFFICIENT
COEFFICIENT
SPHEROIDIZED
AVERAGE







OF MICRO-
OF MICRO-
RATIO OF
DIAMETER OF
ADHESION


SAMPLE
STEEL
FRICTION
FRICTION
CEMENTITE
CEMENTITE
SUPPRESSIVE
CRACK


No.
TYPE
OF FERRITE
OF CEMENTITE
(%)
(μm)
PERFORMANCE
SENSITIVITY
REMARKS























1
A
0.40
0.24
80.4
0.76


INVENTIVE










EXAMPLE


2
B
0.43
0.25
80.4
1.13


INVENTIVE










EXAMPLE


3
C
0.40
0.31
86.5
0.62


INVENTIVE










EXAMPLE


4
D
0.42
0.23
83.8
0.86


INVENTIVE










EXAMPLE


5
E
0.42
0.32
95.5
0.69


INVENTIVE










EXAMPLE


6
F
0.41
0.33
90.0
0.42


INVENTIVE










EXAMPLE


7
G
0.49
0.23
85.4
0.96


INVENTIVE










EXAMPLE


8
H
0.44
0.28
98.7
0.52


INVENTIVE










EXAMPLE


9
I
0.42
0.33
94.8
0.56


INVENTIVE










EXAMPLE


10

J

0.42
0.32
92.6
0.56
X

COMPARATIVE










EXAMPLE


11

K


0.72

0.25
91.4
0.59
X
X
COMPARATIVE










EXAMPLE


12

L

0.42
0.23
81.7
0.85

X
COMPARATIVE










EXAMPLE


13

M

0.42
0.29
85.9
0.73

X
COMPARATIVE










EXAMPLE


14

N

0.41
0.30
75.6
1.04

X
COMPARATIVE










EXAMPLE


15

O

0.42
0.31
90.9
0.36

X
COMPARATIVE










EXAMPLE


16

P

0.41
0.23
82.4
0.54

X
COMPARATIVE










EXAMPLE


17

Q


0.79

0.24
87.7
1.05
X
X
COMPARATIVE










EXAMPLE


18

R


0.79

0.33
92.5
0.55
X
X
COMPARATIVE










EXAMPLE


19

S

0.44
0.27
85.2

2.56


X
COMPARATIVE










EXAMPLE


20

T

0.41
0.31
91.2
0.71

X
COMPARATIVE










EXAMPLE


21

U

0.41
0.28
98.0
0.52

X
COMPARATIVE










EXAMPLE


22

V

0.44
0.31

65.8


0.26


X
COMPARATIVE










EXAMPLE


23

W

0.45
0.25
98.9
0.30

X
COMPARATIVE










EXAMPLE


24

X


0.62

0.28
85.3
0.75
X
X
COMPARATIVE










EXAMPLE


25

Y

0.42
0.27
82.2
0.59

X
COMPARATIVE










EXAMPLE


26

BK


0.69

0.29
80.6
0.92
X

COMPARATIVE










EXAMPLE









As listed in Table 2, Sample No. 1 to Sample No. 9 were each within the range of the present invention, thus being able to obtain good adhesion suppressive performance and crack sensitivity.


On the other hand, in Sample No. 10, the C content of Steel type J was too low, and thus the amount of cementite was insufficient, sufficient lubricity was not able to be obtained, and adhesion to the metal mold occurred during forming. In Sample No. 11, the N content of Steel type K was too high, and thus BN precipitated, the amount of solid-solution B was insufficient, the coefficient of micro-friction of ferrite was low, and adhesion and cracking during the compression test occurred. In Sample No. 12, the Al content of Steel type L was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 13, the B content of Steel type M was too high, and thus boride was formed and a crack originating from the boride is occurred during the compression test. In Sample No. 14, the Mn content of Steel type N was too low, and thus pearlite transformation occurred during cooling in the annealing, the spheroidized ratio of cementite was low, and a crack originating from acicular cementite occurred during the compression test. In Sample No. 15, the P content of Steel type O was too high, and thus segregation of B to the interface between ferrite and cementite was hindered and cracking occurred during the compression test. In Sample No. 16, the Si content of Steel type P was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 77 and Sample No. 18, each B content of Steel type Q and Steel type R was too low, and thus the coefficient of micro-friction of ferrite was low and adhesion and cracking during the compression test occurred. In Sample No. 19, the Si content of Steel type S was too low, and thus cementite became coarse excessively during annealing and a crack originating from the coarse cementite occurred during the compression test. In Sample No. 20, the S content of Steel type T was too high, and thus coarse sulfides being non-metal inclusions were formed and a crack originating from the coarse sulfide occurred during the compression test. In Sample No. 21, the Mn content of Steel type U was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 22, the Cr content of Steel type V was too high, and thus spheroidizing of cementite during annealing was hindered, coarsening of cementite was suppressed, and a crack originating from micro acicular cementite occurred during the compression test. In Sample No. 23, the C content of Steel type W was too high, and thus the amount of cementite was excessive and a crack originating from the cementite occurred during the compression test. In Sample No. 24, the Ti content of Steel type X was too low, and thus BN precipitated, the amount of solid-solution B was insufficient, the coefficient of micro-friction of ferrite was low, and adhesion and cracking during the compression test occurred. In Sample No. 25, the Ti content of Steel type Y was too high, and thus coarse oxides of Ti were formed and a crack originating from the coarse oxide of Ti occurred during the compression test. In Sample No. 26, the Cr content of Steel type BK was too low, and thus BN precipitated, the amount of solid-solution B was insufficient, the coefficient of micro-friction of ferrite was low, and adhesion to the metal mold occurred during forming.


Second Experiment

In a second experiment, hot-rolling of a slab (Steel type Z to BJ) including a chemical composition listed in Table 3 was performed, thereby obtaining a hot-rolled steel sheet having a thickness of 4 mm. In the hot-rolling, the slab heating temperature was 1130° C., the time thereof was 1 hour, the finish rolling temperature was 850° C., and the coiling temperature was 520° C. Then, cooling was performed down to a temperature of less than 60° C., and pickling using sulfuric acid was performed. Thereafter, annealing of the hot-rolled steel sheet was performed to then obtain a hot-rolled annealed steel sheet. In the annealing, the hot-rolled steel sheet was retained for 15 hours at 750° C., and then was cooled down to 650° C. at a cooling rate of 30° C./hr. Subsequently, cooling was performed down to a temperature of less than 60° C. In this manner, various high-carbon steel sheets were manufactured. Blank fields in Table 3 indicate that the content of the element is less than a detection limit, and the balance is Fe and impurities. An underline in Table 3 indicates that the numeric value is out of the range of the present invention.













TABLE 3







STEEL
CHEMICAL COMPONENT (MASS %)
Ac1
Ac3


































TYPE
C
Si
Mn
P
S
Al
N
Ti
Cr
B
Nb
Mo
V
Cu
W
Ta
Ni
Mg
Ca
Y
Zr
La
Ce
(° C.)
(° C.)
REMARKS





Z
0.34
0.52
2.38
0.015
0.0005
0.006
0.007
0.220
1.09
0.0017

0.004











726
811
INVENTIVE




























EXAMPLE


AA
0.35
0.81
2.20
0.013
0.0010
0.080
0.004
0.301
0.83
0.0020
0.192

0.003

0.032

0.047






737
832
INVENTIVE




























EXAMPLE


AB
0.37
0.22
0.31
0.022
0.0017
0.024
0.007
0.078
0.99
0.0011

0.100
0.326

0.163
0.101



0.005
0.002
0.004

741
817
INVENTIVE




























EXAMPLE


AC
0.39
0.11
0.42
0.022
0.0059
0.076
0.005
0.192
0.18
0.0026


0.355

0.395
0.056
0.330
0.114
0.371


0.242
0.311
722
798
INVENTIVE




























EXAMPLE


AD
0.44
0.57
1.45
0.019
0.0024
0.030
0.002
0.189
0.72
0.0013
0.108
0.266

0.114


0.225

0.263
0.467
0.272
0.481

733
805
INVENTIVE




























EXAMPLE


AE
0.47
0.37
0.49
0.018
0.0027
0.008
0.001
0.119
0.46
0.0008
0.313

0.044

0.087


0.441
0.129
0.122
0.339

0.003
734
795
INVENTIVE




























EXAMPLE


AF
0.50
0.26
0.90
0.005
0.0048
0.041
0.003
0.035
0.29
0.0031
0.037




0.002
0.002






727
797
INVENTIVE




























EXAMPLE


AG
0.52
0.65
2.05
0.007
0.0077
0.016
0.001
0.471
1.48
0.0017
0.040
0.258
0.271

0.183






0.002

741
773
INVENTIVE




























EXAMPLE


AH
0.57
0.13
0.51
0.002
0.0062
0.066
0.003
0.169
0.02
0.0025
0.350

0.130
0.383
0.287


0.327
0.007


0.329
0.278
723
772
INVENTIVE




























EXAMPLE


AI
0.57
0.89
2.67
0.001
0.0041
0.020
0.009
0.019
0.91
0.0016
0.080
0.485



0.005
0.491



0.490

0.443
729
798
INVENTIVE




























EXAMPLE


AJ
0.62
0.43
0.78
0.009
0.0078
0.097
0.003
0.365
0.63
0.0033

0.156

0.235
0.002
0.197







733
757
INVENTIVE




























EXAMPLE


AK
0.66
0.69
2.38
0.006
0.0054
0.093
0.007
0.255
0.20
0.0010
0.377
0.049


0.430

0.023
0.005

0.268
0.011
0.006
0.199
723
766
INVENTIVE




























EXAMPLE


AL
0.66
0.63
1.86
0.003
0.0071
0.079
0.001
0.011
1.38
0.0007
0.004

0.019
0.003

0.459







744
781
INVENTIVE




























EXAMPLE


AM

0.22

0.27
2.88
0.023
0.0081
0.018
0.006
0.021
0.83
0.0031
0.081

0.232

0.454
0.086
0.180
0.281

0.128


0.027
714
851
COMPARATIVE




























EXAMPLE


AN
0.34
0.87
2.26
0.006
0.0055
0.064
0.001
0.418
1.27
0.0004
0.082



0.506


0.126







740
819
COMPARATIVE




























EXAMPLE


AO
0.34
0.59
0.99
0.023
0.0021
0.080
0.005
0.296
0.54
0.0033


0.316

0.191

0.447
0.185

0.510





732
825
COMPARATIVE




























EXAMPLE


AP
0.35
0.27
0.97
0.004
0.0051
0.091
0.007
0.311
0.91
0.0006

0.538



0.236







730
811
COMPARATIVE




























EXAMPLE


AQ
0.36
0.99
2.37
0.022
0.0092
0.026
0.006
0.030
0.30

0.0003



0.183
0.471


0.126

0.099

0.107


730
846
COMPARATIVE




























EXAMPLE


AR
0.37
0.78
2.77
0.023
0.0029
0.064
0.002
0.062
0.35
0.0024

0.511


0.473



0.291






719
836
COMPARATIVE




























EXAMPLE


AS
0.38
0.63

0.17

0.022
0.0001
0.091
0.002
0.352
0.27
0.0016
0.196
0.038

0.044

0.005

0.011

0.255


0.013
741
817
COMPARATIVE




























EXAMPLE


AT
0.41
0.71
0.43
0.001
0.0045
0.062
0.004
0.231
0.08
0.0029
0.264

0.160
0.278
0.398
0.425


0.448
0.290
0.029


0.516

738
820
COMPARATIVE




























EXAMPLE


AU
0.42
0.77
1.28
0.016
0.0021
0.027
0.003
0.031
1.18

0.0038

0.001

0.380


0.340



0.496


0.039
755
839
COMPARATIVE




























EXAMPLE


AV
0.43
0.08
2.79
0.020
0.0036
0.011
0.008
0.135
0.71
0.0005







0.523







699
770
COMPARATIVE




























EXAMPLE


AW
0.44
0.90
0.90
0.009
0.0001
0.005
0.004
0.426
1.24
0.0021
0.457


0.532

0.367

0.186
0.120






759
807
COMPARATIVE




























EXAMPLE


AX
0.45
0.54
0.27
0.001
0.0055
0.014
0.002
0.027
0.02
0.0034
0.227
0.008
0.454

0.029

0.189

0.177


0.503


0.192
733
813
COMPARATIVE




























EXAMPLE


AY
0.47
0.93
2.42
0.021
0.0012
0.058
0.004
0.477

1.70

0.0024

0.245


0.257

0.064
0.082

0.221
0.053


754
796
COMPARATIVE




























EXAMPLE


AZ
0.51
0.08

0.14

0.005
0.0010
0.023
0.004
0.016
1.00
0.0032
0.304


0.400
0.394
0.014
0.045
0.137
0.471


0.082
0.433
743
790
COMPARATIVE




























EXAMPLE


BA
0.51
0.75
2.58
0.008
0.0095
0.074
0.003
0.220
0.26
0.0023

0.058
0.365
0.016
0.192





0.505

0.138

0.035
715
785
COMPARATIVE




























EXAMPLE


BB
0.52
0.19
0.82
0.002
0.0091
0.014
0.003
0.282
0.89
0.0024
0.373
0.287
0.303

0.429
0.410
0.208
0.001

0.013
0.054

0.507


734
770
COMPARATIVE




























EXAMPLE


BC
0.54
0.85
2.66
0.002

0.0104

0.023
0.008
0.312
0.41
0.0028


0.468
0.340
0.079



0.024
0.403

0.214
0.022
725
787
COMPARATIVE




























EXAMPLE


BD
0.55
0.26
2.16
0.011
0.0023
0.092
0.001
0.167
1.31
0.0004
0.097

0.030


0.512

0.085







732
770
COMPARATIVE




























EXAMPLE


BE
0.58
0.36
0.86
0.014
0.0073
0.069
0.006

0.009

0.83
0.0016

0.029

0.004
0.018

0.074




0.042

737
782
COMPARATIVE




























EXAMPLE


BF
0.62
0.03
0.93
0.015
0.0100
0.080
0.002
0.027
0.28
0.0020

0.007
0.034

0.201


0.281
0.138

0.344
0.117

716
758
COMPARATIVE




























EXAMPLE


BG
0.66
0.19
1.34
0.028
0.0044
0.018
0.004
0.464
0.80
0.0035

0.235
0.203

0.012

0.147
0.017



0.052

725
731
COMPARATIVE




























EXAMPLE


BH
0.68
0.98
1.94
0.004
0.0094
0.062
0.004
0.070
1.32
0.0006

0.057
0.150

0.045
0.512







746
782
COMPARATIVE




























EXAMPLE


BI
0.68
0.23
2.17
0.019
0.0072
0.006
0.005
0.197
0.70
0.0011
0.475
0.098
0.263
0.427
0.253
0.316
0.455

0.509






712
736
COMPARATIVE




























EXAMPLE


BJ
0.71
0.17
0.52
0.003
0.0064
0.008
0.008
0.046
0.20
0.0021

0.101


0.193
0.013


0.015


0.177
0.022
722
751
COMPARATIVE




























EXAMPLE









Then, in the same manner as in the first experiment, the coefficient of micro-friction of ferrite, and the spheroidized ratio and the average diameter of cementite of each of the high-carbon steel sheets were measured, and further, the evaluation of adhesion suppressive performance and the evaluation of crack sensitivity were performed. Results of them are listed in Table 4. An underline in Table 4 indicates that the item is out of the range of the present invention.

















TABLE 4







COEFFICIENT
COEFFICIENT
SPHEROIDIZED
AVERAGE







OF MICRO-
OF MICRO-
RATIO OF
DIAMETER OF
ADHESION


SAMPLE
STEEL
FRICTION
FRICTION
CEMENTITE
CEMENTITE
SUPPRESSIVE
CRACK


No.
TYPE
OF FERRITE
OF CEMENTITE
(%)
(μm)
PERFORMANCE
SENSITIVITY
REMARKS







31
Z
0.43
0.28
90.8
0.45


INVENTIVE










EXAMPLE


32
AA
0.43
0.23
85.2
0.41


INVENTIVE










EXAMPLE


33
AB
0.41
0.27
80.2
0.98


INVENTIVE










EXAMPLE


34
AC
0.45
0.32
81.4
2.05


INVENTIVE










EXAMPLE


35
AD
0.41
0.28
86.4
0.62


INVENTIVE










EXAMPLE


36
AE
0.43
0.31
82.3
1.24


INVENTIVE










EXAMPLE


37
AF
0.42
0.23
84.5
1.02


INVENTIVE










EXAMPLE


38
AG
0.43
0.30
91.2
0.31


INVENTIVE










EXAMPLE


39
AH
0.42
0.28
82.2
1.71


INVENTIVE










EXAMPLE


40
AI
0.42
0.31
94.1
0.31


INVENTIVE










EXAMPLE


41
AJ
0.43
0.26
91.3
0.89


INVENTIVE










EXAMPLE


42
AK
0.40
0.34
93.9
0.64


INVENTIVE










EXAMPLE


43
AL
0.41
0.24
87.2
0.39


INVENTIVE










EXAMPLE


44

AM

0.43
0.31
90.5
0.45
X

COMPARATIVE










EXAMPLE


45

AN

0.45
0.30
85.4
0.36
X

COMPARATIVE










EXAMPLE


46

AO

0.45
0.25
83.0
0.75

X
COMPARATIVE










EXAMPLE


47

AP

0.44
0.26
86.3
0.64

X
COMPARATIVE










EXAMPLE


48

AQ


0.58

0.25
85.2
0.54
X
X
COMPARATIVE










EXAMPLE


49

AR

0.42
0.31
89.1
0.42

X
COMPARATIVE










EXAMPLE


50

AS

0.40
0.23

79.0

1.39

X
COMPARATIVE










EXAMPLE


51

AT

0.44
0.33
85.7
1.35

X
COMPARATIVE










EXAMPLE


52

AU

0.44
0.32
84.0
0.43

X
COMPARATIVE










EXAMPLE


53

AV


0.73

0.25
98.1
0.56
X

COMPARATIVE










EXAMPLE


54

AW

0.44
0.23
80.9
0.52

X
COMPARATIVE










EXAMPLE


55

AX

0.42
0.27
84.7
1.82

X
COMPARATIVE










EXAMPLE


56

AY

0.41
0.30

64.0


0.24


X
COMPARATIVE










EXAMPLE


57

AZ

0.43
0.23

67.4

1.05

X
COMPARATIVE










EXAMPLE


58

BA

0.43
0.28
92.9
0.57

X
COMPARATIVE










EXAMPLE


59

BB

0.42
0.31
89.6
0.80

X
COMPARATIVE










EXAMPLE


60

BC

0.42
0.22
92.0
0.42

X
COMPARATIVE










EXAMPLE


61

BD

0.46
0.23
95.0
0.46

X
COMPARATIVE










EXAMPLE


62

BE


0.69

0.27
89.6
0.58
X
X
COMPARATIVE










EXAMPLE


63

BF

0.43
0.31
90.6

2.32


X
COMPARATIVE










EXAMPLE


64

BG

0.44
0.22
96.7
0.73

X
COMPARATIVE










EXAMPLE


65

BH

0.42
0.32
85.0
0.37

X
COMPARATIVE










EXAMPLE


66

BI

0.41
0.29
98.9
0.63

X
COMPARATIVE










EXAMPLE


67

BJ

0.42
0.25
88.3
1.64

X
COMPARATIVE










EXAMPLE









As listed in Table 4, Samples No. 31 to No. 43 were each within the range of the present invention, thus being able to obtain good adhesion suppressive performance and crack sensitivity.


On the other hand, in Sample No. 44, the C content of Steel type AM was too low, and thus the amount of cementite was insufficient, sufficient lubricity was not able to be obtained, and adhesion to the metal mold occurred during forming. In Sample No. 45, the Cu content of Steel type AN was too high, and thus a flaw occurred during hot-rolling and adhesion originating from the flaw occurred. In Sample No. 46, the Ca content of Steel type AO was too high, and thus coarse oxides of Ca were formed and a crack originating from the coarse oxide of Ca occurred during the compression test. In Sample No. 47, the Mo content of Steel type AP was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 48, the B content of Steel type AQ was too low, and thus the coefficient of micro-friction of ferrite was low and adhesion and cracking during the compression test occurred. In Sample No. 49, the Nb content of Steel type AR was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 50, the Mn content of Steel type AS was too low, and thus pearlite transformation occurred during cooling in the annealing, the spheroidized ratio of cementite was low, and a crack originating from acicular cementite occurred during the compression test. In Sample No. 51, the Ce content of Steel type AT was too high, and thus coarse oxides of Ce were formed and a crack originating from the coarse oxide of Ce occurred during the compression test. In Sample No. 52, the B content of Steel type AU was too high, and thus boride was formed and a crack originating from the boride occurred during the compression test. In Sample No. 53, the Ni content of Steel type AV was too high, and thus the coefficient of micro-friction of ferrite was high and adhesion occurred. In Sample No. 54, the V content of Steel type AW was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 55, the Zr content of Steel type AX was too high, and thus coarse oxides of Zr were formed and a crack originating from the coarse oxide of Zr occurred during the compression test. In Sample No. 56, the Cr content of Steel type AY was too high, and thus spheroidizing of cementite during annealing was hindered, coarsening of cementite was suppressed, and a crack originating from micro acicular cementite occurred during the compression test. In Sample No. 57, the Mn content of Steel type AZ was too low, and thus pearlite transformation occurred during cooling in the annealing, the spheroidized ratio of cementite was low, and a crack originating from acicular cementite occurred during the compression test. In Sample No. 58, the Y content of Steel type BA was too high, and thus coarse oxides of Y were formed and a crack originating from the coarse oxide of Y occurred during the compression test. In Sample No. 59, the La content of Steel type BB was too high, and thus coarse oxides of La were formed and a crack originating from the coarse oxide of La occurred during the compression test. In Sample No. 60, the S content of Steel type BC was too high, and thus coarse sulfides being non-metal inclusions were formed and a crack originating from the coarse sulfide occurred during the compression test. In Sample No. 61, the W content of Steel type BD was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 62, the Ti content of Steel type BE was too low, and thus EN precipitated, the amount of solid-solution B was insufficient, the coefficient of micro-friction of ferrite was low, and adhesion and cracking during the compression test occurred. In Sample No. 63, the Si content of Steel type BE was too low, and thus cementite became coarse excessively and a crack originating from the coarse cementite occurred during the compression test. In Sample No. 64, the P content of Steel type BG was too high, and thus segregation of B to the interface between ferrite and cementite was hindered and cracking occurred during the compression test. In Sample No. 65, the Ta content of Steel type BH was too high, and thus the ductility of ferrite was low and a crack originating from transgranular fracture of ferrite occurred during the compression test. In Sample No. 66, the Mg content of Steel type BI was too high, and thus coarse oxides of Mg were formed and a crack originating from the coarse oxide of Mg occurred during the compression test. In Sample No. 67, the C content of Steel type BJ was too high, and thus the amount of cementite was excessive and a crack originating from the cementite occurred during the compression test.



FIG. 1 illustrates the relationship between the coefficient of micro-friction of ferrite and the B content of Samples No. 1 to No. 25 and No. 31 to No. 67 except for Samples No. 11, No. 51, No. 53, and No. 62. As illustrated in FIG. 1, when the B content is 0.0004% or more, the coefficient of micro-friction of ferrite is significantly low as compared to the case when it is less than 0.0004%.


Third Experiment

In a third experiment, hot-rolling and annealing were performed under various conditions on the steel types that were within the range of the present invention (Steel types A to I and Steel types Z to AL) out of the steel types used in the first experiment and the steel types used in the second experiment so as to manufacture high-carbon steel sheets. Conditions of them are listed in Table 5 to Table 7. An underline in Table 5 to Table 7 indicates that the numeric value is out of the range of the present invention.













TABLE 5









CONDITIONS IN HOT-ROLLING
CONDITIONS IN ANNEALING


















SLAB HEATING
FINISH ROLLING
COILING
RETENTION
RETENTION
COLLING



SAMPLE
STEEL
TEMPERATURE
TEMPERATURE
TEMPERATURE
TEMPERATURE
TIME
RATE


No.
TYPE
(° C.)
(° C.)
(° C.)
(° C.)
(hr)
(° C./hr)
REMARKS





71
A
1116
871
540

786

51.4
56.7
COMPARATIVE










EXAMPLE


72
B
1149
841
646
745
18.4
58.6
INVENTIVE










EXAMPLE


73
C
1113
879

706

747
 9.7
26.7
COMPARATIVE










EXAMPLE


74
D
1006
940
681
757
34.7
33.6
INVENTIVE










EXAMPLE


75
E
1149
889
605
756
2.2
13.9
COMPARATIVE










EXAMPLE


76
F
993
902
554
759
 3.6
30.7
COMPARATIVE










EXAMPLE


77
G
1068
891
684
742
26.8
 3.8
INVENTIVE










EXAMPLE


78
H
1044
874
685
736
56.2
53.2
INVENTIVE










EXAMPLE


79
I
1083
845
590
748
46.3
40.7
INVENTIVE










EXAMPLE


80
Z
1120
914
616
751
 6.5
 1.3
INVENTIVE










EXAMPLE


81
AA
1122
880

714

765
43.0
58.9
COMPARATIVE










EXAMPLE


82
AB
1113
844
583
752
55.3
 2.7
INVENTIVE










EXAMPLE


83
AC
1088
863
695
749
 7.6
38.0
INVENTIVE










EXAMPLE


84
AD
1065
850
547
741
18.3

68.1

COMPARATIVE










EXAMPLE


85
AE
1095
904
680
750
36.5
48.6
INVENTIVE










EXAMPLE


86
AF
1118
949
521

776

57.9
 7.5
COMPARATIVE










EXAMPLE


87
AG
1024
859

435

766
58.7
 5.5
COMPARATIVE










EXAMPLE


88
AH
1078
874
620
754
18.8
21.3
INVENTIVE










EXAMPLE


89
AI
1028
861
615
753
 3.1
21.2
INVENTIVE










EXAMPLE


90
AJ
1136
915
689
767
46.8
27.6
INVENTIVE










EXAMPLE


91
AK
1098
936
645
760
37.1
 8.1
INVENTIVE










EXAMPLE


92
AL
1099
901
691
754
29.7
12.7
INVENTIVE










EXAMPLE




















TABLE 6









CONDITIONS IN HOT-ROLLING
CONDITIONS IN ANNEALING


















SLAB HEATING
FINISH ROLLING
COILING
RETENTION
RETENTION
COLLING



SAMPLE
STEEL
TEMPERATURE
TEMPERATURE
TEMPERATURE
TEMPERATURE
TIME
RATE


No.
TYPE
(° C.)
(° C.)
(° C.)
(° C.)
(hr)
(° C./hr)
REMARKS


















101
A
1104
873
527

721

38.3
32.0
COMPARATIVE










EXAMPLE


102
B
1060

983

560
757
56.8
17.3
COMPARATIVE










EXAMPLE


103
C
1129
865
625
732
4.9
42.7
INVENTIVE










EXAMPLE


104
D

1175

863
548
767
12.6
30.7
COMPARATIVE










EXAMPLE


105
E
1109
875
632
749
4.6
40.7
INVENTIVE










EXAMPLE


106
F
1088
865
677
768
23.0
 2.3
INVENTIVE










EXAMPLE


107
G
1142
869
536
736
5.5

62.3

COMPARATIVE










EXAMPLE


108
H
1064
848
640
739
14.8
29.0
INVENTIVE










EXAMPLE


109
I
1064
847
621
745
7.8
24.5
INVENTIVE










EXAMPLE


110
Z
1007
878
656
747
48.2
 2.9
INVENTIVE










EXAMPLE


111
AA
1051
943
699
768
6.2
 1.2
INVENTIVE










EXAMPLE


112
AB

1158

908
526
760
6.2
 7.3
COMPARATIVE










EXAMPLE


113
AC
1131

823

532
761
47.9
16.2
COMPARATIVE










EXAMPLE


114
AD
1047
847
605
730
22.5
25.2
INVENTIVE










EXAMPLE


115
AE
1080
862
648
752
26.8
31.7
INVENTIVE










EXAMPLE


116
AF
1102
885
666
741
17.0
42.8
INVENTIVE










EXAMPLE


117
AG
1050
932
601
770
32.6
 1.9
INVENTIVE










EXAMPLE


118
AH
1025
875
540

718

26.3
41.3
COMPARATIVE










EXAMPLE


119
AI
1078
936
625
750
17.1
58.1
INVENTIVE










EXAMPLE


120
AJ
1079
881
671
764
9.7
28.7
INVENTIVE










EXAMPLE


121
AK
1084
867
641
735
27.8
 4.5
INVENTIVE










EXAMPLE


122
AL
1116
890
531
742
4.5
 9.3
INVENTIVE










EXAMPLE




















TABLE 7









CONDITIONS IN HOT-ROLLING
CONDITIONS IN ANNEALING


















SLAB HEATING
FINISH ROLLING
COILING
RETENTION
RETENTION
COLLING



SAMPLE
STEEL
TEMPERATURE
TEMPERATURE
TEMPERATURE
TEMPERATURE
TIME
RATE


No.
TYPE
(° C.)
(° C.)
(° C.)
(° C.)
(hr)
(° C./hr)
REMARKS





131
A
1096
870
511
764
54.5
10.2
INVENTIVE










EXAMPLE


132
B
1097
886
479
768
18.7
0.4
COMPARATIVE










EXAMPLE


133
C
1107
835
502
762
 6.1
56.6
INVENTIVE










EXAMPLE


134
D
1022
857
464
755
 4.8
45.2
INVENTIVE










EXAMPLE


135
E
1087

801

453
743
17.6
54.7
COMPARATIVE










EXAMPLE


136
F
1069
858
576
761
34.0
49.8
INVENTIVE










EXAMPLE


137
G
1032
931

444

738
35.9
16.5
COMPARATIVE










EXAMPLE


138
H
1096
843
497
749

62.6

42.7
COMPARATIVE










EXAMPLE


139
I
1046
895
536
754
48.1
24.5
INVENTIVE










EXAMPLE


140
Z
1123
920
489
755
2.6
58.5
COMPARATIVE










EXAMPLE


141
AA
1082
865
495
731
34.8
33.3
INVENTIVE










EXAMPLE


142
AB
1058
924
482
749
26.5
24.3
INVENTIVE










EXAMPLE


143
AC
1123
904
524
743
35.3
35.6
INVENTIVE










EXAMPLE


144
AD
1077
877
498
741
10.4
0.8
COMPARATIVE










EXAMPLE


145
AE
1008
939
574
753
22.1
28.7
INVENTIVE










EXAMPLE


146
AF
1034

962

482
751
41.0
 7.4
COMPARATIVE










EXAMPLE


147
AG
1133
916
457
732
 4.5
24.0
INVENTIVE










EXAMPLE


148
AH
1037
884
561
748
59.0
 9.4
INVENTIVE










EXAMPLE


149
AI
979
847
508
752
59.9
 4.6
COMPARATIVE










EXAMPLE


150
AJ
1126
933
479
748

68.3

 3.3
COMPARATIVE










EXAMPLE


151
AK
1138
893
598
752
26.9
 3.2
INVENTIVE










EXAMPLE


152
AL
1063
865
584
746
40.3
 2.6
INVENTIVE










EXAMPLE









Then, in the same manner as in the first experiment, the coefficient of micro-friction of ferrite, and the spheroidized ratio and the average diameter of cementite of each of the high-carbon steel sheets were measured, and further, the evaluation of adhesion suppressive performance and the evaluation of crack sensitivity were performed. Results of them are listed in Table 8 to Table 10. An underline in Table 8 to Table 10 indicates that the item is out of the range of the present invention.
















TABLE 8









AVERAGE






COEFFICIENT
COEFFICIENT
SPHEROIDIZED
DIAMETER



OF MICRO-
OF MICRO-
RATIO OF
OF
ADHESION


SAMPLE
FRICTION
FRICTION
CEMENTITE
CEMENTITE
SUPPRESSIVE
CRACK


No.
OF FERRITE
OF CEMENTITE
(%)
(μm)
PERFORMANCE
SENSITIVITY
REMARKS







71

0.72

0.33
86.8

2.25

X
X
COMPARATIVE









EXAMPLE


72
0.43
0.31
87.9
1.15


INVENTIVE









EXAMPLE


73

0.64

0.27

78.3

0.63
X
X
COMPARATIVE









EXAMPLE


74
0.44
0.28
88.3
0.90


INVENTIVE









EXAMPLE


75

0.63

0.24
84.3

0.29

X
X
COMPARATIVE









EXAMPLE


76

0.59

0.24
90.3
0.42
X
X
COMPARATIVE









EXAMPLE


77
0.49
0.28
80.9
0.99


INVENTIVE









EXAMPLE


78
0.44
0.31
94.3
0.54


INVENTIVE









EXAMPLE


79
0.43
0.29
93.1
0.59


INVENTIVE









EXAMPLE


80
0.48
0.28
80.8
0.98


INVENTIVE









EXAMPLE


81

0.71

0.23

75.4

2.12
X
X
COMPARATIVE









EXAMPLE


82
0.44
0.22
87.1
0.65


INVENTIVE









EXAMPLE


83
0.47
0.34
82.0
1.25


INVENTIVE









EXAMPLE


84

0.61

0.34

62.3

1.04
X
X
COMPARATIVE









EXAMPLE


85
0.46
0.29
91.2
0.33


INVENTIVE









EXAMPLE


86

0.73

0.25
83.6

2.36

X
X
COMPARATIVE









EXAMPLE


87

0.64

0.23
98.9
1.16
X

COMPARATIVE









EXAMPLE


88
0.47
0.30
93.0
0.92


INVENTIVE









EXAMPLE


89
0.45
0.28
94.8
0.63


INVENTIVE









EXAMPLE


90
0.45
0.27
97.1
0.43


INVENTIVE









EXAMPLE


91
0.44
0.32
96.5
0.68


INVENTIVE









EXAMPLE


92
0.45
0.28
90.4
0.46


INVENTIVE









EXAMPLE























TABLE 9









AVERAGE






COEFFICIENT
COEFFICIENT
SPHEROIDIZED
DIAMETER



OF MICRO-
OF MICRO-
RATIO OF
OF
ADHESION


SAMPLE
FRICTION
FRICTION
CEMENTITE
CEMENTITE
SUPPRESSIVE
CRACK


No.
OF FERRITE
OF CEMENTITE
(%)
(μm)
PERFORMANCE
SENSITIVITY
REMARKS







101

0.72

0.31
82.3
0.77
X
X
COMPARATIVE









EXAMPLE


102

0.61

0.22
82.8
1.18
X

COMPARATIVE









EXAMPLE


103
0.42
0.26
81.3
0.61


INVENTIVE









EXAMPLE


104

0.71

0.26
92.2
0.89
X

COMPARATIVE









EXAMPLE


105
0.44
0.24
95.3
0.69


INVENTIVE









EXAMPLE


106
0.42
0.30
94.9
0.45


INVENTIVE









EXAMPLE


107

0.61

0.31

64.1

0.95
X
X
COMPARATIVE









EXAMPLE


108
0.43
0.32
95.4
0.53


INVENTIVE









EXAMPLE


109
0.42
0.26
89.8
0.56


INVENTIVE









EXAMPLE


110
0.44
0.34
88.0
1.01


INVENTIVE









EXAMPLE


111
0.44
0.34
84.2
2.07


INVENTIVE









EXAMPLE


112

0.69

0.25
89.6
0.63
X

COMPARATIVE









EXAMPLE


113

0.59

0.32
85.5
1.29
X
X
COMPARATIVE









EXAMPLE


114
0.47
0.23
84.0
1.03


INVENTIVE









EXAMPLE


115
0.48
0.28
92.8
0.33


INVENTIVE









EXAMPLE


116
0.45
0.30
90.0
1.73


INVENTIVE









EXAMPLE


117
0.44
0.26
99.8
0.34


INVENTIVE









EXAMPLE


118

0.63

0.25
85.9
0.83
X
X
COMPARATIVE









EXAMPLE


119
0.47
0.23
93.9
0.66


INVENTIVE









EXAMPLE


120
0.45
0.28
95.9
0.41


INVENTIVE









EXAMPLE


121
0.46
0.24
87.9
0.65


INVENTIVE









EXAMPLE


122
0.39
0.25
80.6
0.43


INVENTIVE









EXAMPLE























TABLE 10









AVERAGE






COEFFICIENT
COEFFICIENT
SPHEROIDIZED
DIAMETER



OF MICRO-
OF MICRO-
RATIO OF
OF
ADHESION


SAMPLE
FRICTION
FRICTION
CEMENTITE
CEMENTITE
SUPPRESSIVE
CRACK


No.
OF FERRITE
OF CEMENTITE
(%)
(μm)
PERFORMANCE
SENSITIVITY
REMARKS







131
0.39
0.32
83.6
0.81


INVENTIVE









EXAMPLE


132

0.68

0.33
97.2

2.45

X
X
COMPARATIVE









EXAMPLE


133
0.40
0.24
89.9
0.63


INVENTIVE









EXAMPLE


134
0.40
0.24
87.2
0.86


INVENTIVE









EXAMPLE


135

0.66

0.31
88.1
0.74
X
X
COMPARATIVE









EXAMPLE


136
0.44
0.24
91.6
0.45


INVENTIVE









EXAMPLE


137

0.59

0.26
86.5
0.99
X

COMPARATIVE









EXAMPLE


138

0.66

0.22
92.5

2.55

X
X
COMPARATIVE









EXAMPLE


139
0.38
0.32
97.5
0.59


INVENTIVE









EXAMPLE


140

0.60

0.22
82.7

0.22

X
X
COMPARATIVE









EXAMPLE


141
0.40
0.27
85.9
2.07


INVENTIVE









EXAMPLE


142
0.40
0.33
86.0
0.64


INVENTIVE









EXAMPLE


143
0.40
0.23
89.1
1.27


INVENTIVE









EXAMPLE


144

0.54

0.27
81.6

2.38

X
X
COMPARATIVE









EXAMPLE


145
0.43
0.31
93.5
0.33


INVENTIVE









EXAMPLE


146

0.62

0.24
82.4
1.77
X

COMPARATIVE









EXAMPLE


147
0.37
0.31
81.0
0.30


INVENTIVE









EXAMPLE


148
0.40
0.32
90.4
0.93


INVENTIVE









EXAMPLE


149

0.72

0.33
94.5
0.68
X
X
COMPARATIVE









EXAMPLE


150

0.58

0.29
84.7

2.46

X
X
COMPARATIVE









EXAMPLE


151
0.43
0.23
94.5
0.67


INVENTIVE









EXAMPLE


152
0.44
0.25
80.4
0.46


INVENTIVE









EXAMPLE









As listed in Table 8, Samples No. 72, No. 74, No. 77 to No. 80, No. 82, No. 83, No. 85, and No. 88 to No. 92 were each within the range of the present invention, thus being able to obtain good adhesion suppressive performance and crack sensitivity. As listed in Table 9, Samples No. 103, No. 105, No. 106, No. 108 to No. 111, No. 114 to No. 117, and No. 120 to No. 122 were each also within the range of the present invention, thus being able to obtain good adhesion suppressive performance and crack sensitivity. As listed in Table 10, Samples No. 131, No. 133, No. 134, No. 136, No. 139, No. 141 to No. 143, No. 145, No. 147, No. 148, No. 151, and No. 152 were each also within the range of the present invention, thus being able to obtain good adhesion suppressive performance and crack sensitivity.


On the other hand, in Sample No. 71, the annealing retention temperature was too high, and thus volume expansion was large, a hot-rolled coil was uncoiled to cause abrasions, and a tightening mark caused by a tightening band also occurred. Further, the thickness of the film of crystals of B greatly varied and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. Further, cementite became coarse excessively and a crack originating from the coarse cementite occurred during the compression test. In Sample No. 73, the coiling temperature was too high, and thus coarse lamellar pearlite was formed in the hot-rolled steel sheet, spheroidizing of cementite during annealing was hindered, and the spheroidized ratio of cementite was low. Further, large irregularities were formed with removal of scales and the coefficient of micro-friction of ferrite was large. Therefore, adhesion and cracking during the compression test occurred. In Sample No. 75, the annealing retention time was too short, and thus the coefficient of micro-friction of ferrite was large and the average diameter of cementite was small. Therefore, adhesion and cracking during the compression test occurred. In Sample No. 76, the slab heating temperature was too low, and thus segregations of B, Mn, and others were not eliminated and the coefficient of micro-friction of ferrite was large. Therefore, adhesion and cracking during the compression test occurred. In Sample No. 81, the coiling temperature was too high, and thus adhesion and cracking during the compression test occurred similarly to Sample No. 73. In Sample No. 84, the cooling rate was too high, and thus pearlite transformation occurred during cooling and a crack originating from acicular cementite occurred during the compression test. Further, a good film of crystals of B was not formed on the surface of the high-carbon steel sheet, the coefficient of micro-friction of ferrite was high, and adhesion occurred. In Sample No. 86, the annealing retention temperature was too high, and thus adhesion and cracking during the compression test occurred, similarly to Sample No. 81. In Sample No. 87, the coiling temperature was too low, and thus as a result of removal of scales, the surface of the steel sheet became rough and adhesion occurred.


In Sample No. 101, the annealing retention temperature was too low, and thus the segregation of B to the interface between ferrite and austenite was suppressed, the coefficient of micro-friction of ferrite was large, and adhesion occurred. Further, the segregation of B to the interface between ferrite and cementite was also suppressed and cracking occurred during the compression test. In Sample No. 102, the finish rolling temperature was too high, and thus large irregularities were formed with removal of scales and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. In Sample No. 104, the slab heating temperature was too high, and thus B atoms were oxidized during slab heating and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. In Sample No. 107, the cooling rate was too high, and thus pearlite transformation occurred during cooling and a crack originating from acicular cementite occurred during the compression test. Further, a good film of crystals of B was not formed on the surface of the high-carbon steel sheet, the coefficient of micro-friction of ferrite was high, and adhesion occurred. In Sample No. 112, the slab heating temperature was too high, and thus adhesion occurred, similarly to Sample No. 104. In Sample No. 113, the finish rolling temperature was too low, and thus anisotropy of the structure was strong and a crack originating from a nonuniform structure occurred during the compression test. Further, as a result of removal of scales, the surface of the steel sheet became rough and adhesion occurred. In Sample No. 118, the annealing retention temperature was too low, and thus adhesion and cracking during the compression test occurred, similarly to Sample No. 101.


In Sample No. 132, the cooling rate was too low, and thus the thickness of the film of crystals of B greatly varied and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. Further, cementite became coarse excessively and a crack originating from the coarse cementite occurred during the compression test. In Sample No. 135, the finish rolling temperature was too low, and thus anisotropy of the structure was strong and a crack originating from a nonuniform structure occurred during the compression test. Further, as a result of removal of scales, the surface of the steel sheet became rough and adhesion occurred. In Sample No. 137, the coiling temperature was too low, and thus as a result of removal of scales, the surface of the steel sheet became rough and adhesion occurred. In Sample No. 138, the annealing retention time was too long, and thus volume expansion was large, a hot-rolled coil was uncoiled to cause abrasions, and a tightening mark caused by a tightening band also occurred. Further, the thickness of the film of crystals of B greatly varied and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. Further, cementite became coarse excessively and a crack originating from the coarse cementite occurred during the compression test. In Sample No. 140, the annealing retention time was too short, and thus the coefficient of micro-friction of ferrite was large and the average diameter of cementite was small. Therefore, adhesion and cracking during the compression test occurred. In Sample No. 144, the cooling rate was too low, and thus adhesion and cracking during the compression test occurred, similarly to Sample No. 132. In Sample No. 146, the finish rolling temperature was too high, and thus, large irregularities were formed with removal of scales and the coefficient of micro-friction of ferrite was large. Therefore, adhesion occurred. In Sample No. 149, the slab heating temperature was too low, and thus segregations of B, Mn, and others were not eliminated and the coefficient of micro-friction of ferrite was large. Therefore, adhesion and cracking during the compression test occurred. In Sample No. 150, the annealing retention time was too long, and thus adhesion and cracking during the compression test occurred, similarly to Sample No. 138.



FIG. 7 illustrates the relationship between the coefficient of micro-friction of ferrite and the B content in the samples out of the examples in the first experiment or third experiment. As illustrated in FIG. 7, when the B content is 0.0008% or more, the coefficient of micro-friction of ferrite is much lower as compared to the case when it is less than 0.0008%.


INDUSTRIAL APPLICABILITY

The present invention may be utilized in, for example, manufacturing industries and application industries of high-carbon steel sheets used for various steel products, such as a driving system component for automobile, a saw, a knife, and others.

Claims
  • 1. A high-carbon steel sheet, comprising: a chemical composition represented by, in mass %:C: 0.30% to 0.70%,Si: 0.07% to 1.00%,Mn: 0.20% to 3.00%,Ti: 0.010% to 0.500%,Cr: 0.01% to 1.50%,B: 0.0004% to 0.0035%,P: 0.025% or less,Al: 0.100% or less,S: 0.0100% or less,N: 0.010% or less,Cu: 0.500% or less,Nb: 0.000% to 0.500%,Mo: 0.000% to 0.500%,V: 0.000% to 0.500%,W: 0.000% to 0.500%,Ta: 0.000% to 0.500%,Ni: 0.000% to 0.500%,Mg: 0.000% to 0.500%,Ca: 0.000% to 0.500%,Y: 0.000% to 0.500%,Zr: 0.000% to 0.500%,La: 0.000% to 0.500%,Ce: 0.000% to 0.500%, andbalance: Fe and impurities; anda structure represented by:a spheroidized ratio of cementite: 80% or more; andan average diameter of cementite: 0.3 μm to 2.2 μm, whereina coefficient of micro-friction of ferrite on a surface of the steel sheet is less than 0.5.
  • 2. The high-carbon steel sheet according to claim 1, wherein the high-carbon steel sheet contains one or more selected from the group consisting of:Nb: 0.001% to 0.500%;Mo: 0.001% to 0.500%;V: 0.001% to 0.500%;W: 0.001% to 0.500%;Ta: 0.001% to 0.500%;Ni: 0.001% to 0.500%;Mg: 0.001% to 0.500%;Ca: 0.001% to 0.500%;Y: 0.001% to 0.500%;Zr: 0.001% to 0.500%;La: 0.001% to 0.500%; andCe: 0.001% to 0.500%.
  • 3. A method of manufacturing a high-carbon steel sheet, comprising: hot-rolling of a slab so as to obtain a hot-rolled steel sheet;pickling of the hot-rolled steel sheet; andannealing of the hot-rolled steel sheet after the pickling,the slab comprising a chemical composition represented by, in mass %:C: 0.30% to 0.70%,Si: 0.07% to 1.00%,Mn: 0.20% to 3.00%,Ti: 0.010% to 0.500%,Cr: 0.01% to 1.50%,B: 0.0004% to 0.0035%,P: 0.025% or less,Al: 0.100% or less,S: 0.0100% or less,N: 0.010% or less,Cu: 0.500% or less,Nb: 0.000% to 0.500%,Mo: 0.000% to 0.500%,V: 0.000% to 0.500%,W: 0.000% to 0.500%,Ta: 0.000% to 0.500%,Ni: 0.000% to 0.500%,Mg: 0.000% to 0.500%,Ca: 0.000% to 0.500%,Y: 0.000% to 0.500%,Zr: 0.000% to 0.500%,La: 0.000% to 0.500%,Ce: 0.000% to 0.500%, andbalance: Fe and impurities, whereinin the hot-rolling,the slab is heated at a temperature of 1000° C. or more and less than 1150° C.,a finish rolling temperature is 830° C. or more and 950° C. or less, anda coiling temperature is 450° C. or more and 700° C. or less, andthe annealing comprises:retaining the hot-rolled steel sheet at a temperature of 730° C. or more and 770° C. or less for 3 hours or more and 60 hours or less; andthen cooling the hot-rolled steel sheet down to 650° C. at a cooling rate of 1° C./hr or more and 60° C./hr or less.
  • 4. The method of manufacturing the high-carbon steel sheet according to claim 3, wherein the slab contains one or more selected from the group consisting of:Nb: 0.001% to 0.500%;Mo: 0.001% to 0.500%;V: 0.001% to 0.500%;W: 0.001% to 0.500%;Ta: 0.001% to 0.500%;Ni: 0.001% to 0.500%;Mg: 0.001% to 0.500%;Ca: 0.001% to 0.500%;Y: 0.001% to 0.500%;Zr: 0.001% to 0.500%;La: 0.001% to 0.500%; andCe: 0.001% to 0.500%.
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2014/077544 10/16/2014 WO 00