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Steel Plate For Cold Forging And Process For Producing Same

Abstract: Disclosed is a steel plate for cold forging which comprises a hot-rolled steel plate, the hot-rolled steel plate containing, in terms of mass%, 0.13-0.20% C, 0.01-0.8% Si, 0.1-2.5% Mn,0.003-0.030% P, 0.0001-0.008% S, 0.01-0.07% Al, 0.0001-0.02% N, and 0.0001-0.0030% O, with the remainder comprising Fe and incidental impurities, and having a value A shown by equation (1) of 0.0080 or less and a thickness of 2-25 mm. In a cross-section parallel to the rolling direction of the hot-rolled steel plate, the amount in areal percentage of pearlite bands having a length of 1 mm or longer which are present in the area ranging from (4/10)t to (6/10)t, where t is the thickness of the plate, is not more than the value K shown by equation (2). Value A = O%+S%+0.033Al% (1) Value K = 25.5×C%+4.5×Mn%-6 (2)

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Patent Information

Application #
Filing Date
23 July 2012
Publication Number
02/2014
Publication Type
INA
Invention Field
METALLURGY
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2021-04-07
Renewal Date

Applicants

NIPPON STEEL & SUMITOMO METAL CORPORATION
6-1, MARUNOUCHI 2-CHOME, CHIYODA-KU, TOKYO 100-8071, JAPAN

Inventors

1. MASAYUKI ABE
c/o Nippon Steel Corporation  6-1  Marunouchi 2-chome  Chiyoda-ku  Tokyo 100-8071
2. KENGO TAKEDA
c/o Nippon Steel Corporation  6-1  Marunouchi 2-chome  Chiyoda-ku  Tokyo 100-8071
3. SHUJI YAMAMOTO
c/o Nippon Steel Corporation  6-1  Marunouchi 2-chome  Chiyoda-ku  Tokyo 100-8071
4. YASUSHI TSUKANO
c/o Nippon Steel Corporation  6-1  Marunouchi 2-chome  Chiyoda-ku  Tokyo 100-8071
5. SHINICHI YAMAGUCHI
c/o Nippon Steel Corporation  6-1  Marunouchi 2-chome  Chiyoda-ku  Tokyo 100-8071

Specification

DESCRIPTION
STEEL PLATE FOR COLD FORGING AND PROCESS FOR PRODUCING SAME
5 TECHNICAL FIELD
[0001]
The present invention relates to a steel plate for cold forging which is an
appropriate material for producing parts such as engines and transmissions of automobiles,
through cold forging (plate press forging) and a method for producing the same. In detail,
10 the present indention relates to a steel plate for cold forging which inlcludes a hot-rolled
steel plate having a small anisotropy in workability, a steel plate for cold forging which
further includes a surface-treated film having excellent lubricity enough to endure cold
forging, and a method for producing the same. '
The present application claims priority on Japanese Patent Application No.
15 2010-013446 filed on January 25, 2010 and Japanese Patent'Application No.2010-013447
filed on January 25, 2010, the contents of which are incorporated herein by reference.
BACKGROUND ART
[0002]
20 As a working process in which metallic materials such as iron and steel materials
and stainless steels are plastically deformed, mainly, there are hot forging in which a steel
material is molded while being heated and cold forging in which a steel.material is molded
using a mold at room temperature.
In recent years, efforts have been being made to decrease weights of automobile
25 bodies in order to reduce amount of CO2 emissions from the automobiles from the
viewpoint of global environmental protection, and a use of a high-strength steel plate
having a strength of 440 MPa or more is proceeded. In addition, in automobile
companies and parts makers, parts which were conventionally produced through hot
forging are produced through cold press forging so as to simplify production steps.
5 Simplification of steps saves energy and decreases costs in the production process; and
thereby, efficiency of the process is improved. Particularly, from the viewpoint of `
improving the efficiency of the production process, a production method in which a plate
material is subjected to cold press forging without conducting hot forging, that is, plate
press forging is applied to a process of producing parts which were conventionally formed
10 by subjecting a material such as a steel bar and the like to hot forging and cutting work so
as to secure part accuracy.
[0003]
However, in the case where a 440 MPa or higher-class plate material is subjected
to cold plate press forging, a problem that material cracks occur is notably caused
15 compared to hot forging. In addition, uneven formability due to rolling-induced
anisotropy in the plate surface is observed. The uneven formability does not occur easily
in an axially symmetric material_suchasa^steetbar. _ Therefre a lot ofprahle^ns that need
to be solved such as the occurrence of cracking in a specific direction and unevenness in
shape after working. At the moment, it is necessary to change a design to a shape in
20 which cracking does not occur, and it is also necessary to carry out a step in which uneven
portions occurred after drawing, so-called ear portions, are cut off. Therefore, there is a
demand for a material having better workability and uniform characteristics.
[0004]
As described above, in the process of producing parts, it is necessary to improve
25 workability which is required for a material in order to greatly simplify the process steps
compared to the related art. Particularly, in order to change the material from a steel bar
to a steel plate, there has been a demand for an improvement of anisotropy between a
rolling direction and a direction perpendicular thereto.
[0005]
5 Particularly, unlike pressing of a steel plate having a thickness of approximately 1
mm in the related art, cold plate press forging is performed on a hot-rolled steel plate
having a thickness of approximately 2 mm to 25 mm as a material for parts such as
engines, transmissions, and the hlce, and the hot-rolled steel plate is thicker than a steel
plate used for body parts in the related art. Therefore, ultimate deformability that is
10 required during working is an important characteristic:
[0006]
As a high-strength hot-rolled steel plate that is excellent in ultimate deformability
and shape fixability, a hot-rolled steel plate is prdposed which is obtained by controlling
texture and anisotropy in ductility (for example, refer to Patent Document 1). However,
15 Patent Document 1 does not specifically disclose cold plate press forging.
[0007]
Jn_addition cold fosgingattains extremelyiilgh productivity andAimensional
accuracy. In addition, a worked product worked through cold forging has advantages
such as improved abrasion properties, enhanced strength due to cold work hardening, and
20 the like. However, in cold forging, a metallic material is pressed while the metallic
material is brought into contact with a mold or the like at a high surface pressure. As a
result, temperature at the contact portion between the metallic material and the mold
becomes a relatively high temperature (approximately 300°C or higher) due to friction
between the metallic material and the mold during pressing. Therefore, in the case where
25 lubricity between the metallic material and the mold is not sufficient, such as the case
where a metallic material that is not surface-treated or the like is subjected to cold forging,
there are cases in which seizure or galling occurs between the metallic material (material)
and the mold. Seizure or galling causes local breakage or abrupt abrasion of the mold;
and thereby, not only there are cases in which the service life of the mold is greatly
5 shortened, but also there are cases in which working becomes impossible.
[0008]
In order to prevent seizure or galling, generally, a metallic material to be
subjected to cold forging is subjected to a surface treatment for applying lubricity to a
surface of the metallic material (hereinafter often referred to as "lubrication treatment').
10 As the lubrication treatment, a phosphate treatment (bonderizing treatment) has been
known in the related art in which aphosphate film composed of a phosphate compound
(zinc phosphate, manganese phosphate, calcium phosphate, iron phosphate, or the like) is
formed on a surface of a metallic material.
[0009]
15 Performance of the phosphate treatment to prevent seizure and galling is
relatively strong. However, as described above, due to the recent environmental
_ measures, cold forging is_mom commonly carried ouUhan workings thatsnvohc large-------
shape deformation, such as hot forging accompanied by large energy consumption and
cutting wottk that causes a large amount of material loss, and there is a demand for stricter
20 plastic working in cold forging. From the above-described viewpoint, a composite film
has been widely used which father includes a layer composed of a metallic soap (for
example, sodium stearate or the like) laminated on the phosphate film. The composite
film has an excellent performance to prevent seizure and galling even under strict abrasion
conditions due to pressing with a high surface pressure during cold forging.
25 [0010]
According to the lubrication treatment to form the composite film, the metallic
soap reacts with the phosphate film; and thereby, favorable lubricity is exhibited.
However, the lubrication treatment requires a lot of cumbersome treatment steps such as a
cleaning step, a reaction step in which the metallic soap and the phosphate film are reacted
5 with each other, and the like. In the reaction step, it is also necessary to control a
treatment fluid, a temperature during the reaction, and the like. In addition, since the
lubrication treatment is a batch treatment, there is a problem in that the productivity
degrades. In addition, the lubrication treatment to form the composite film has problems
such as a treatment of a waste liquid generated during the treatment or the like, and the
10 lubrication treatment is not preferred from the viewpoint of environmental protection.
[0011]
Therefore, in recent years, a variety of lubrication treatment processes have been
proposed for replacing the lubrication treatment to form the composite film.
[0012]
15 For example, Patent Document 2 proposes a lubricant composition or the like in
which a water-soluble polymer or a water-based emulsion thereof is included as a base
material, anda solidlubricantand an agent forihrming a chemical conversion coating
film are further included. However, with regard to the lubricant composition or the like
of Patent Document 2, lubricity and performance to prevent seizure and galling that are
20 comparable to those of the above-described composite film cannot be obtained.
[0013]
In addition, for example, Patent Document 3 proposes a water-based lubricant for
cold plastic working of metal. The water-based lubricant is composed of (A) a
water-soluble inorganic salt, (B ) a solid lubricant, (C) at least one oil component selected
25 from a mineral oil, an animal or plant fat, and a synthetic oil, (D) a surfactant, and (E)
water, and the solid lubricant and the oil component are uniformly dispersed and
emulsified respectively. However, since the oil component is emulsified, the lubricant
obtained by the above-described technique is unstable for industrial use, and favorable
lubricity is not stably exhibited.
5 [0014]
In contrast to the above-described matters, for example, Patent Document 4
proposes a metallic material for plastic working which includes a concentration-gradient
type two-layer lubricant film composed of a base layer and a lubricant layer. Patent
Document 4 describes that a film having favorable lubricity can be generated through a
10 simple treatment.
[0015]
However, in the technique of Patent Document 4, adhesion between the film and
a metal which is a base material is insufficient; grid thereby, the film easily separates from
the metal during working, particularly during strong working. Since a mold and the
15 metal come into contact with each other at portions where the film separates, there is a
problem in that seizure easily occurs at the separation portions.
PRIOR ART DOCUMENT
Patent Document
20 [0016]
Patent Document 1: Japanese Unexamined Patent Application, First Publication
No. 2005-15854
Patent Document 2: Japanese Unexamined Patent Application, First Publication
No. S52-20967
25 Patent Document 3: Japanese Unexamined Patent Application, First Publication
No. H10-8085
Patent Document 4: Japanese Unexamined Patent Application, First Publication
No. 2002-264252
5 DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0017]
The present invention has been made in consideration of the above-described
circumstances, and the present invention aims to provide a steel plate for cold forging and
10 a method for producing the same. The steel plate for cold forging can improve
workability in a process where parts for engines and transmissions are produced through
cold forming, so-called plate press forging, and the parts for engines and transmissions
were conventionally manufactured through hot forging and the like.
15 Means for Solving the Problems
[0018]
Thepresentin entors carriedozLthoroughstudiesso as to solve the
above-described problems. As a result, the inventors found that reduction of anisotropy
in workability cannot be realized simply by changing rolling conditions, and it is
20 important to consistently control and optimize components and relevant structures through
a hot rolling step. Specifically, an amount of oxides, a content of S, and a content of Al
during smelting are defined, and conditions from. hot rolling to coiling are optimized.
Thereby, the structure is controlled . As a result, it was revealed that the above-described
controlling of the structure can solve the above-described problems and stably improve
25 anisotropy in workability. Particularly, in the case where plastic deformability degrades
due to portions at which non-metallic inclusions and carbides that are so-called pearlite
bands are present in a dense state in a central area of a plate thickness, anisotropies in
workability in a rolling direction and in a direction perpendicular thereto increase. The
fact that the pearlite bands take a form that extends lengthwise in the rolling direction due
5 to rolling facilitates anisotropy in plastic deformability. It was found that an increase in
the anisotropy in workability can be suppressed by defining a relationship between an area
percentage and components of the pearlite bands. In addition, it was also found that an
elongation rate of the pearlite bands in the rolling direction and a fraction of the pearlite
bands can be controlled by controlling the rolling conditions of the hot rolling, cooling
10 conditions, and coiling conditions in a series.
In addition, thorough studies were also carried out regarding a surface-treated
film. As a result, it was found that excellent lubricity can be applied to a steel plate by
providing a concentration-gradient type surface-treated film and controlling thicknesses of
respective constituent layers. The concentration-gradient type surface-treated film is
15 provided by a simple treatment process that does not cause a problem regarding waste
liquid treatment. The concentration-gradient type surface-treated film is composed of
three layers otla adhesion layer for securing adhesionioAhe steel plate which .serves as a
base material, a base layer for holding a lubricant, and a lubricant layer for improving
lubricity. ,_
20 [0019]
A steel plate for cold forging according to an aspect of the invention includes a
hot-rolled steel plate, wherein the hot-rolled steel plats includes: in terms of percent by
mass, C: 0.13% to 0.20%; Si: 0.01% to 0.8%; Mn: 0.1% to 2.5%; P: 0.003% to 0.030%; S:
0.0001% to 0.008%; Al: 0.01% to 0.07%; N: 0.0001% to 0.02%; and O: 0.0001% to
25 0.0030%, with a remainder being Fe and inevitable impurities, and an A value represented
by the following formula (1) is in a range of 0.0080 or less. A thickness of the
hot-rolled steel plate is in a range of 2 mm to 25 mm, and an area percentage of pearlite
bands having lengths of 1 mm or more is in a range of not more than a IC value
represented by the following formula (2) in a region of 4/lot to 6/lot when a plate
5 thickness is indicated by tin a cross section of a plate thickness that is parallel to a rolling
direction of the hot-rolled steel plate.
Avalue =0%+S%+0.033A1%•• (1)
K value = 25.5 x C%+4.5 x Mn% - 6 "(2)
In the steel plate for cold forging according the aspect of the invention, the
10 hot-rolled steel plate may further include, in terms of percent by mass, one or more
selected from a group consisting of: Nb: 0.001% to 0.1%; Ti: 0.001% to 0.05%; V:
0.001% to 0.05%; Ta: 0.01% to 0.5%; and W: 0.01% to 0.5%.
The hot-rolled steel plate may further include, in terms of percent by mass, Cr:
0.01 % to 2.0%, and the area percentage of the pearlite bands having lengths of 1 mm or
15 more may be in a range of not more than a K' value represented by the following formula
(3).
evalue= 15 r C% 4.5 x-Mn%-+ 3 2 x Cr% - 3.3 (3^
The hot-rolled steel plate may further include, in terms of percent by mass, one or
more selected from a group consisting of: Ni: 0.01% to 1.0%; Cu: 0.01% to 1.0%; Mo:
20 0.005% to 0.5%; and B: 0.0005% to 0.01%.
The hot-roiled steel plate may further include, in terms of percent by mass, one or
more selected from a group consisting of: Mg: 0.0005% to 0.003%; Ca: 0.0005% to
0.003%; Y: 0.001% to 0.03%; Zr: 0.001% to 0.03%; La: 0.001% to 0.03%; and Ce:
0.001% to 0.03%.
25 The steel plate for cold forging may further include a surface-treated film
10
provided on either one or both of main surfaces of the hot-rolled steel plate, and the
surface-treated film may include a component originating from a silanol bond represented
by Si-O-X (X represents a metal that is a component of the hot-rolled steel plate), a
high-temperature resin, an inorganic acid salt, and a lubricant. The surface-treated film
5 may have a concentration gradient of each component in a film thickness direction so as to
have a concentration-gradient type three-layer structure that can be identified to be three
layers of an adhesion layer, a base layer, and a lubricant layer situated in series from a side
of an interface between the surface-treated film and the hot-rolled steel plate. The
adhesion layer may be a layer that includes a largest amount of the component originating
10 from the silanol bond among the three layers, and a thickness of the adhesion layer may be
in a range of 0.1 nm to 100 nm. The base layer may be a layer that includes largest
amounts of the high-temperature resin and the inorganic acid salt among the three layers,
the amount of the inorganic acid salt in the base layer may be in a range of 1 part by mass
to 100 parts by mass with respect to 100 parts by mass of the high-temperature resin, and a
15 thickness of the base layer may be in a range of 0.1 μm to 15 μm. The lubricant layer
may be a layer that includes a largest amount of the lubricant among the three layers, and a
- thickness-ofithe lubricant layer-ma-y-be-in-a-range-of 0.1 jim-to l0 μm:-AA-ratio of-the------
thickness of the lubricant layer to the thickness of the base layer may be in a range of 0.2
to 10.
20 The inorganic acid salt may be at least one compound selected from a group
consisting of phosphate, borate, silicate, molybdate, and tungstate.
The high-temperature resin may be a polyimide resin.
The lubricant may be at least one compound selected from a group consisting of
polytetrafluoroethylene, molybdenum disulfide, tungsten disulfide, zinc oxide, and
25 graphite.
11
[0020]
A method for producing a steel plate for cold forging according to an aspect of
the invention includes: heating a slab at a temperature of 1150°C to 1300°C; subjecting the
heated slab to rough rolling at a temperature of 1020°C or higher so as to make a rough
5 bar; subjecting the rough bar to finishing rolling under a condition where a finishing
temperature is in a range of Ae3 or higher so as to make a rolled material; after the
finishing rolling, subjecting the rolled material to air cooling for 1 second to 10 seconds;
after the air cooling,, cooling the rolled material at a cooling rate of 10°C/s to 70°C/s to a
coiling temperature; and coiling the cooled rolled material at the coiling temperature of
10 400°C to 580°C so as to make a hot-rolled steel plate. The slab includes: in terms of
percent by mass, C: 0.13% to 0.20%; Si: 0.01% to 0.8%; Mn: 0.1% to 2.5%; P: 0.003% to
0.030%; S: 0.0001% to 0.006%, Al: 0.01% to 0.07%, N: 0.0001% to 0.02%, and 0:
0.0001% to 0.0030% with a remainder being Fe and inevitable impurities, and an A value
represented by the following formula (1) is in a range of 0.0080 or less. The rough
15 rolling includes a first rolling and a second rolling that is carried out 30 seconds or more
after an end of the first rolling. The first rolling is carried out under conditions where a
temperature isi a range of 1 20°C or higher and a sum olfrolling reductioarates is in a
range of 50% or more, and the second rolling is carried out under conditions where a
temperature is in a range of 1020°C or higher and a sum of rolling reduction rates is in a
20 range of 15% to 30%.
Avalue =0%+S%+0.033A1%... (1)
The method for producing a steel plate for cold forging according to the aspect of
the invention may further include: coating a water-based surface treatment fluid including
a water-soluble silane coupling agent, a water-soluble inorganic acid salt, a water-soluble
12
high-temperature resin, and a lubricant on either one or both of main surfaces of the
hot-rolled steel plate so as to form a coated film; and drying the coated film so as to form a
surface-treated film on either one or both of the main surfaces of the hot-rolled steel plate.
Meanwhile, Ae3 refers to a value computed from the following formula.
5 Ae3(°C)=910-372xC%+29.8xSi%- 30.7 x Mn% + 776.7 x P% - 13.7 x
Cr% - 78.2Ni%
Effects of the Invention
[0021]
10 According to the aspect of the invention, it is possible to provide a steel plate for
cold forging which has a 440 MPa-class to 780 MPa-class high strength and is used as a
material for automobile parts. In addition, the steel plate for cold forging has a relatively
thick thickness of 2 mm or more, and reduced anisotropies in workability in a rolling
direction and in a direction perpendicular thereto. In detail, it is possible to provide a
15 steel plate (hot-rolled steel plate) for cold forging which has small anisotropy in
workability so that anisotropy in ultimate deformability (ultimate deformation ratio)
during-cold-press-forging working is in a range-o".-9 or more; and thereby, cracking can
be prevented during press forging working.
III addition, in the case where the above-described concentration-gradient type
20 surface-treated film is further included which is composed of three layers of the adhesion
layer, the base layer, and the lubricant layer, it is possible to provide a steel plate for cold
forging which can be produced-by a simple treatment step and is preferable even from the
viewpoint of global environmental protection. In addition, the steel plate for cold forging
has excellent lubricity and excellent performance to prevent seizure and galling.
25 Therefore, according to the steel plate for cold forging according to the aspect of
13
the invention, workability can be improved in cold forming, so-called plate press forging.
Thereby, parts for engines or transmissions which were produced by hot forging and the
like in the related art can be produced by plate press forging. Therefore, the steel plate
for cold forging according to the aspect of the invention is effective for simplifying steps
5 such as production steps of automobile parts, and the like and reducing costs of the steps;
and thereby, the steel plate for cold forging according to the aspect of the invention
contributes to energy saving.
BRIEF DESCRIPTION OF THE DRAWINGS
10 [0022]
FIG I is a view showing a relationship between A values and anisotropies
(4c/r L) in ultimate deformability with regard to hot-rolled steel plates containing 0.15%C
0.2%Si - 0.3%Mn - 0.5%Cr - 0.002%B as basic components.
FIG 2 is a view showing a relationship between A values and anisotropies
15 (^c/4L) in ultimate deformability with regard to hot-rolled steel plates containing 0.14%C
- 0.25%Si - 1.45%Mn as basic components.
FIG 3-is-a view-showing-relationship between-area percentages (%) of pearlite
bands in a central portion of a plate thickness and anisotropies (4c/+L) in ultimate
deformability with regard to hot-rolled steel plates having chemical components of
20 0.19%C - 0.15%Si - 0.66%Mn - 0.65%Cr - 0.015%P - 0.0017%S - 0.024%Al - 0.0018%O
- 0.0016%B.
FIG. 4 is a view showing a relationship between area percentages (%) of pearlite
bands in a central portion of a plate thickness and anisotropies (4c/^L) in ultimate
deformability with regard to hot-rolled steel plates having chemical components of
14
0.15%C - 0.2%Si - 1.51%Mn - 0.02%P - 0.0015%S - 0.032%Al - 0.0021%0.
FIG. 5A is a micrograph (at 50-fold magnification) of a hot-rolled steel plate of
Example 1.
FIG 5B is a micrograph of the hot-rolled steel plate of Example 1, and is a
5 photograph of a dotted line region in FIG. 5A at 100-fold magnification.
FIG. 5C is a micrograph of the hot-rolled steel plate of Example 1, and is a
photograph of a dotted line region in FIG 5B at 200-fold magnification.
FIG 6 is an explanatory view schematically showing a configuration of a steel
plate for cold forging according to a second embodiment.
10 FIG 7A is an explanatory view for explaining a spike test method.
FIG. 7B is a view showing shapes of a test specimen before and after working by
the spike test method.
FIG 8 is a view showing a relationship between ratios of (an area percentage of
pearlite bands) / (IC value or IC' value) and anisotropies (^c/^L) in ultimate deformability.
15
BEST MODE FOR CARRYING OUT THE INVENTION
[0023]
Hereinafter, preferable embodiments of the invention will be described in detail
with reference to the accompanying drawings. Meanwhile, in the present specification
20 and the drawings, components (constituents) having substantially the same function will
be given the same reference sign so that duplicate description will not be made.
(First embodiment)
[Steel plate for cold forging according to the first embodiment]
The steel plate for cold forging according to the first embodiment is composed of
25 a hot-rolled steel plate. The hot-rolled steel plate has small anisotropy in workability and
15
is excellent in workability. The hot-rolled steel plate will be described below.
Firstly, 50 kg of steel ingots having the following chemical components were
melted under vacuum in a laboratory in order to investigate influences of the components
of the hot-rolled steel plate on characteristics.
5 (i) A steel ingot containing 0.15%C - 0.2%Si - 0.3%Mn - 0.5%Cr - 0.002%B as
basic components and having a variety of contents of S; 0, and Al. (ii) A steel ingot
containing 0.14%C - 0.25%Si - 1.45%Mn as basic components and having a variety of
contents of S, 0, and Al.
The respective steel ingots were heated to 1200°C, and subsequently, the steel
10 ingots were subjected to hot-rolling under conditions Where a thickness. was decreased
from 100 mm to 10 mm. After the hot rolling was ended at 900°C, the steel ingots were
subjected to air-cooling for 3 seconds. Next, the steel ingots were cooled to 500°C at a
cooling rate of 30°C/s. Thereafter, the steel ingots were retained in a furnace at 500°C
for 1 hour, and then the steel ingots were cooled in the furnace so as to simulate an actual
15 coiling step.
A tension test specimen of a round bar having a diameter of 8 mm was taken
along a rolling direction of each off rabtained hotbed steel p ates. Similarly, a
tension test specimen of a round bar having a diameter of 8 mm was taken along a
direction perpendicular with respect to the rolling direction. Tensile tests (tension tests)
20 were carried out using the test specimens. Ultimate deformabilities were measured from
cross section shrinkage rates of the test specimens after the tests. The ultimate
deformability in the rolling direction was indicated by ^L, the ultimate deformability in
the direction perpendicular with respect to the rolling direction was indicated by +c, and a
relationship between ratios (fie/4L) and the components was investigated. Here, the
16
ultimate deformability is calculated from the following formula. In addition, a value of
the ratio (^c/4L) approaching to 1 means small anisotropy in workability.
Ultimate deformability ^ = In (So/S)
(Herein, So refers to a cross-sectional area of the test specimen before the tension
5 test, and S refers to a cross-sectional area of a broken portion after the tension test)
[0024]
FIG. 1 is a view showing a relationship between A values and anisotropies
(4c/4L) in ultimate deformability with regard to the hot-rolled steel plates having the
chemical components of the above-described (i). In addition, FIG. 2 is a view showing a
10 relationship between A values and anisotropies (+c/^L) in ultimate deformability with
regard to the hot-rolled steel plate having the chemical components of the above-described
(ii).
As a result of regression analyses regard ing a relationship between the ultimate
deformabilities in the rolling direction and either one of contents of 0 (0%), contents of S
15 (S%), and contents of Al (Al%), the A value represented by the following formula (1) was
determined.
fA-value =O07o+S%+ D.033A1°
(Here, 0%, S%, and AIM represent contents (% by mass) of 0, S, and Al
included ii the hot-rolled steel plate, respectively.)
20 In the relational formula that represents the A value, the coefficients (1) of the
content of S and the content of 0 are large compared to the coefficient (0.033) of the
content of Al; and therefore, it is found that influences of the content of S and the content
of 0 on the ultimate deformability in the rolling direction are large. Generally, it is
considered that uneven distribution of inclusions in interfaces and the like influence the
17
ultimate deformability. In the relational formula that represents the A value, it is
considered as follows. The fact that the coefficients of the content of Al, the content of S,
and the content of 0 are different shows that the influences on the uneven distribution of
the inclusions vary by the components.
5 [0025]
As shown in FIG. 1, it is found that, as the A value calculated from the content of
0 (0%), the content of S (S%), and the content of Al (Al%) increases, the relative ratio
(4)c/4L) of the ultimate deformability 4 c in the direction perpendicular with respect to the
rolling direction to the ultimate deformability ^L in the rolling direction decreases; and
10 therefore, anisotropy in workability increases. As shown in FIG. 1, it was determined
that, in the case where the A value is in a range of 0.008 or less, the cross section
shrinkage rate in the direction perpendicular to the rolling direction becomes a value close
to the cross section shrinkage rate in the rolling direction, the ratio of ^c/^L becomes in a
range of 0.9 or more; and therefore, a steel plate having small anisotropy in workability
15 can be produced.
Similarly, even in FIG. 2, a correlation between the anisotropies (4c/4L) in
ultimate efor ility and the A values was obtained. - It was confirmed that, in the case
where in the case where the A value is in a range of 0.007 or less, the cross section
shrinkage rate in the direction perpendicular to the rolling direction becomes a value close
20 to the cross section shrinkage rate in the rolling direction, the ratio of +c/4 L becomes in a
range of 0.9 or more; and therefore, a steel plate having small anisotropy in workability
can be produced.
[0026]
It is considered that the total amount of non-metallic inclusions is decreased by
18
decreasing the content of oxygen (0%); and thereby, the anisotropy is decreased. In
addition, it is considered that in the case where an excessive content of Al is not added, an
amount of coarse alumina-based non-metallic inclusion; and thereby, the anisotropy is
decreased. Furthermore, it was confirmed that influences of S on MnS and the like can
5 be controlled in conjunction with 0 and Al by decreasing the content of S (S%).
[0027]
In addition, a relationship between production conditions and anisotropies
(4c/4L) in ultimate deformability was investigated using slabs (billets) having the
following chemical components.
10 (iii) A slab having components of 0.19%C - 0.15%Si - 0.66%Mn - 0.65%Cr -
0.015%P - 0.0017%S - 0.024%Al - 0.0018%O - 0.0016%B.
(iv) A slab having components of 0.15%C - 0.2%Si - 1.51 %Mn - 0.02%P -
0.0015%S - 0.032%Al - 0.0021%0.
As a result, it was found that, other than the chemical components, there is a
15 relationship between a presence state of pearlite bands'and anisotropy in ultimate
deformability. Particularly, in a hot-rolled steel plate produced from a slab using an
actual-machine presence fraction (area percentage) ofpearlltgbands-extending in a
rolling direction is high in a central portion of a plate thickness. In the central area in a
region of 4/10t to 6/10t in which the plate thickness is indicated by t, the higher the
20 presence fraction of pearlite bands having a length of 1 mm or longer is, the more the
ultimate deformability (+c) in the direction perpendicular to the rolling direction decreases.
As a result, the anisotropy in ultimate deformability becomes less than 0.9; and therefore,
anisotropy in workability becomes large.
Here, the pearlite band refers to a band-shaped aggregate having a length of 1 mm
25 or longer in which pearlites having thicknesses of 5 μm or more in a plate thickness are
19
arranged in a rolling direction at intervals of 20 pm or less. The presence fraction (area
percentage) (%) of the pearlite bands was measured by the following method. A
cross-sectional portion of the plate thickness that is parallel to the rolling direction was
taken. The cross-sectional portion was subjected to a polishing treatment, and then, the
5 cross-sectional portion was immersed in a Nital solution (a solution including
approximately 5% of nitric acid with the remainder being alcohol); and thereby, pearlite
emerged. Next, with regard to the central portion of the plate thickness in a region of
4/1Ot to 6/101 with respect to the plate thickness t, the structure was photographed using an
optical microscope (at a 100-fold magnification), and the obtained images were connected.
10 The connected images were subjected to image analysis using an image analysis software
(WinROOF Vcr. 5.5.0 manufactured by lblitani Corporation); and thereby, the area
percentage of the pearlite bands was obtained. The obtained results are shown in FIGS. 3
and 4. In the chemical component systems of the above-described (iii) and (iv), it was
determined that, in the case where the area percentage of the pearlite bands having sizes of
15 1 mm or more is in a range of 4.6% or less in the central portion of the plate thickness, the
anisotropy in ultimate deformability becomes 0.9 or more; and therefore, the anisotropy in
workability-becomes-small
[0028]
The inventors further investigated a relationship between the above-described
20 area percentage of the pearlite bands and the ultimate deformability. As a result, it was
found that the area percentage of the pearlite bands for maintaining the anisotropy in
ultimate deformability in a range of 0.9 or more highly relates to the chemical components.
Relationships between the area percentage of the pearlite bands and the contents of a
variety of components were subjected to regression analysis. As a result, it was found
25 that, with regard to the component system of the present embodiment, in the case where
20
the area percentage of the pearlite bands is in a range of not more than the K value
indicated by the following formula (2), the anisotropy in ultimate deformability becomes
0.9 or more. In addition, it was found that, in the case where Cris included, and the area
percentage of the pearlite bands is in a range of not more than the K' value indicated by
5 the following formula (3), the anisotropy in ultimate deformability becomes 0.9 or more.
Kvalue =25.5xC%+4.5xMn%-6.•.(2)
K'value=15xC%+4.5xMn%+3.2xCr%-3.3...(3)
(Herein, C%, Mn%, and Cr% refer to the contents (% by mass) of C, Mn, and Cr
included in the hot-rolled steel plate, respectively.)
10 It, found from the relational formulae representing the K value and the IC' value
that formation of the pearlite bands is strongly affected by the contents of C, Mn, and Cr
which are basic components. In the component system of the present embodiment, it is
important to set the chemical components and the production conditions so that the area
percentage of the pearlite bands becomes the K value or less and the K' value or less.
15 [0029]
The chemical components of the hot-rolled steel plate in the present embodiment
are set-based on-the above-described finding. Reasons why-the components and
composition of the hot-rolled steel plate in the present embodiment are limited will be
described below. Meanwhile, "%" refers to "% by mass."
20 [0030]
(Chemical components)
C: 0.13%to 0.20%
C is an important component for securing a strength of the hot-rolled steel plate.
However, machinability is required to work (form) members for automobiles which are
25 targets of the present embodiment. In the case where the content of Cis less than 0.13%,
21
the amount of carbides decreases ; and thereby, machinability deteriorates. Therefore,
0.13% or more of Cis required so as to secure machinability. On the other hand, in the
case where the content of C exceeds 0.20%, workability degrades in the hot -rolled steel
plate in a state in which nothing is carried out thereon after production . Therefore, the
5 content of Cis set to be in a range of 0.13%to 0 .20%. The content of Cis preferably in
a range of 0.13% to 0.18 %, and more preferably in a range of 0.14% to 0.17%.
[0031]
Si: 0.01% to 0.8%
Si is a solid-solution strengthening element; and therefore , Si can enhance the
10 strength of the steel plate at a relatively low cost. In addition, it is necessary to add a
small content of Si on consideration of a relationship between C and scale flaws.
Therefore, the content of Si is set to 0.01% or more ; however, in the case where the
content of Si exceeds 0.8%, the effect is saturated . Therefore, the content of Si is set to
be in a range of 0.01 % to 0 . 8%. The content of Si is preferably in a range of 0.03% to
15 0.5%, and more preferably in a range of 0.1% to 0.3%.
[0032]
Mn: D- to to2S°1o
Mn is a solid-solution strengthening element; and therefore, Mn is an important
component for securing a desired high tensile strength. In the case where the content of
20 Mn is less than 1.0%, it is necessary to contain other strengthening elements in order to
secure a necessary strength; and thereby, the costs increase, which is not preferable. On
the other hand, as the content of Mn increases, pearlite bands become liable to be
generated due to segregation of Mo. In the case where the content of Mn exceeds 2.5%,
segregation to a center portion becomes significant in a slab (billet); and as a result,
25 workability of the hot-rolled steel plate in a direction perpendicular to a rolling direction
22
degrades even when the steel plate is produced by the production method of the present
embodiment. Therefore, the content of Mn is set to be in a range of 0.1% to 2.5%. The
content of Mn is preferably in a range of more than 0.3% to 2.0% or less, more preferably
in a range of 0.4% to 1.7%, and most preferably in a range of 0.6% to 1.5%.
5 [0033]
P: 0.003% to 0.030%
P is a solid-solution strengthening element; and therefore , P is an element that can
enhance the strength of the steel plate at a relatively low cost. However, it is not
preferable to include an excessive content of P from the viewpoint of toughness.
10 Therefore, the content of Pis set to be in a range of 0.03% or less. In addition, from the
viewpoint of refining, setting of the content of P to be in a range of less than 0.003% leads
to an increase in costs. Therefore, the content of Pis set to be in a range of 0.003% to
0.030%. The content of Pis preferably in a range of 0.003% to 0.020%, and more
preferably in a range of 0.005% to 0.015%.
15 [0034]
S: 0.0001% to 0.008%
lshucIuded ina steel as an impurityrand S forms-MnS. MnS causes
degradation of durability and toughness of the steel plate which determines workability of
cold working; Particularly, since MnS increases anisotropy in workability, it is necessary
20 to reduce the content of S from the viewpoint of reducing the amount of MnS. Therefore,
the content of S is set to be in a range of 0.008% or less. In addition, setting of the
content of S to be in a range of less than 0.0001% leads to a great increase in refining
costs. Therefore, the content of S is set to be in a range of 0.0001% to 0.008%. The
content of S is preferably in a range of 0.0001% to 0.005%, and more preferably in a
25 range of 0.0001% to 0.004%.
23
[0035]
Al: 0.01% to 0.07%
Al is an element that is added for deoxidization of a steel; however, in the case
where the content of Al is less than 0.01%, deoxidization effect is not sufficient. On the
5 other hand, in the case where the content of Al exceeds 0.07%, the deoxidization effect is
saturated. In addition, in a process in which a curved slab is produced through
continuous casting, when the obtained slab is subjected to bending correction, Al
facilitates cracking due to precipitation of AIN, and this results in an economic
disadvantage. Therefore, the content of Al is set to be in a range of 0.01% to 0.07%.
10 The content of Al is preferably in a range of 0.01% to 0.04%.
[0036]
N: 0.0001%to 0.02%
When bonding correction of the slab is carried out using a curved continuous
casting facility, precipitation of N as a nitride causes cracking in the slab. Therefore, the
15 content of N is set to be in a range of 0.02% or less. In addition, reducing of the content
of N to less than 0.0001% leads to an increase in the refining costs. Therefore, the
content_of N is set-to be in mange of 0.0001% to 0.02_ The content_ofiN is preferably_
in a range of 0.0001% to 0.01%, and more preferably in a range of 0.0001% to 0.005%.
[0037]
20 0: 0.0001 % to 0.0030%
Since some of 0 atoms exist as oxides, 0 has an influence on the workability of
cold working, and 0 causes degradation of durability and toughness. In the case where
the content of 0 increases, inclusions become large. In addition, in the case where the
inclusions aggregate, the ductility lowers greatly. Therefore, the content of 0 is set to be
25 in a range of 0.0001% to 0.0030%. It is desirable that the content of 0 be reduced as
24
much as possible, and the content of 0 is preferably in a range of 0.0001% to 0.0025%,
and more preferably in a range of 0.0001% to 0.0020%.
[0038]
In the present embodiment, as a result of considering both of the chemical
5 components and the production conditions, it was confirmed that degradation of the
workability can be suppressed by fulfilling the following formula. Therefore, the content
of oxygen (0%) is adjusted according to the content of S (S%) and the content of Al
(Al%) so as to fulfill the following formula. The A value in the following formula is,
preferably in a range of 0.0070 or less. The lower limit of the A value is preferably
10 0.0010. Setting of the A value to be in a range of less than 0.0010 leads to a great
increase in the refining costs, which is not preferable.
A value = 0% + S% + 0.033A1% 5 0.0080
[0039]
Next, components that the hot-rolled steel plate of the embodiment may
15 selectively contain according to necessity will be described.
[0040]
-Nb: 0-001%-to-0.1 %
Nb has effects of improving the strength of the steel plate and improving the
toughness of the steel plate through a grain refining action. In the present embodiment,
20 Nb may be included as a selective element. However, in the case where the content of
Nb is less than 0.003%, the above-described effects cannot be sufficiently obtained. On
the other hand, in the case where the content of Nb exceeds 0.1 %, the effects are saturated,
and this leads to an economic disadvantage. In addition, in the case where an excessive
content of Nb is included, recrystallization behaviors during hot rolling are delayed.
25 Therefore, the content of Nb is set to be in a range of 0.001% to 0.1%. The content of
25
Nb is preferably in a range of 0.003% to 0.1%.
[0041]
Ti: 0.001%to 0.05%
Ti may be added from the viewpoint of fixing of N, and Ti contributes to
5 embrittlement of the slab and stabilization of a material . However, in the case where the
content of Ti exceeds 0.05%, the effects are saturated. In addition , in the case where the
content of Ti is 10 ppm or less, the effects cannot be obtained . Therefore, the content of
Ti is set to be in a range of 0.001 % to 0.05%.
[0042]
10 V: 0.001%to 0.05%
V strengthens the hot-rolled steel plate through precipitation of carbonitr-ides.
Therefore, V may be added according to necessity . In the case where the content of V is
less than 0 . 001%, the effect is small. In addition , in the case where the content of V
exceeds 0 . 05%, the effect is saturated . Therefore, the content of V is set to be in a range
15 of 0.001% to 0.05%.
[0043]
0.01% to_Q.54%
Similarly to Nb and V, Ta is an element that forms carbonitrides, and Ta is
effective for prevention of coarsening of crystal grains, improvement of toughness, and the
20 like; and therefore, Ta may be added according to necessity. In the case where the
content of Ta is less than 0.01%, the effect of the addition is small; and therefore, the
lower limit of the content of Ta is set to 0.01%. In the case where the content of I aexceeds
0.5%, the effect of the addition is saturated, and the costs increase. In addition,
an excessive amount of carbides are formed; and thereby, recrystallization and the like are
25 delayed. As a result, anisotropy in workability is increased. Therefore, the upper limit
26
of the content of Ta is set to 0.5%.
[0044]
W: 0.01% to 0.5%
Similarly to Nb, V, and Ta, W is an element that forms carbonitrides, and W is
5 effective for prevention of coarsening of crystal grains, improvement of toughness, and the
like, and W maybe added according to necessity. In the case where the content of 'W is
less than 0.01%, the effect of the added W is small; and therefore, the lower limit of the
content of W is set to 0.01%. In the case where the content of W exceeds 0.5%, the
effect of the added W is saturated, and the costs increase. In addition, an excessive
10 amount of carbides are formed; and thereby, recrystallization and the like are delayed.
As a result, anisotropy in workability is increased. Therefore, the upper limit of the
content of W is set to 0.5%.
[0045]
Cr: 0.01% to 2.0%
15 Cr is effective for strengthening the steel plate, particularly, Cr can be used as an
alternative element which is an alternative to Mn, and Cr may be added as a selective
element However, in the case where the content- Cris less than 0.01%o,_the effect is
not exhibited. In the case where the content of Cr exceeds 2.0%, the effect is saturated in
the present embodiment. Therefore, the content of Cr is set to be in a range of 0.01% to
20 2.0%. The content of Cris preferably in a range of more than 0.1% to 1.5%, and more
preferably in a range of more than 0.3% to 1.1 %.
[0046]
Ni: 0.01% to 1.0%
Ni is effective for the toughness and strengthening of the steel plate, and Ni may
25 be added as a selective element. However, in the case where the content of Ni is less
27
than 0.01%, the effect is not exhibited. In the case where the content of Ni exceeds 1.0%,
the effect is saturated in the present embodiment. Therefore, the content of Ni is set to be
in a range of 0.01% to 1.0%.
[0047]
5 Cu: 0.01% to 1.0%
Similarly to Cr and Ni, Cu is effective for securing the strength of the steel plate,
and Cu may be added as a selective element. However, in the case where the content of
Cu is less than 0.01%, the effect is not exhibited. In the case where the content of Cu
exceeds 1.0%, the effect is saturated in the present embodiment. Therefore, the content
10 of Cu is set to be in a range of 0.01 % to 1.0%.
[0048]
Mo: 0.005% to 0.5%
Mo is an effective element for strengthening of the structure and improvement in
toughness, and Mo may be added as a selective element. In the case where the content of
15 Mo is less than 0.001 %, the effect is small. In addition, in the case where the content of
Mo exceeds 0.5%, the effect is saturated in the present embodiment. Therefore, the
content of Mn_is set tohe uiarange_of0_ 10S%io 0.5%.
[0049]
B: 0.0001%to 0.01%
20 B improves hardenability when B is added at a small content . In addition, B is
an effective element for suppressing pearlite transformation so as to reduce the amount of
pearlite bands, and B may be added according to necessity . In the case where the content
of B is less than 0 .0001%, the effect of the added B is not exhibited; and therefore, the
lower limit of the content of B is set to 0.0005%. In addition , in the case where the
25 content of B exceeds 0.01 %, forgeability degrades ; and thereby, cracking is caused in the
28
slab. Therefore, the upper limit of the content of B is set to 0.01%. The content of B is
preferably in a range of 0.0005% to 0.005%.
[0050]
Mg: 0.0005% to 0.003%
5 Mg is an effective element for controlling configurations of oxides and sulfides
when Mg is added at a small content, and Mg may be added according to necessity. ° In
the case where the content of Mg is less than 0.0005%, the effect cannot be obtained. In
addition, in the case where the content of Mg exceeds 0.003%, the effect is saturated.
Therefore, the content of Mg is set to be in a range of 0.0005% to 0.003%.
10 [0051]
Ca: 0.0005% to 0.003%
Similarly Mg, Ca is an effective element for controlling the configurations of
oxides and sulfides when Ca is added at a small content, and Ca may be added according
to necessity. In the case where the content of Ca is less than 0.0005%, the effect cannot
15 be obtained. In addition, in the case where the content of Ca exceeds 0.003%, the effect
is saturated. Therefore, the content of Ca is set to be in a range of 0.0005% to 0.003%.
- [ff052]
Y. 0.001%to 0.03%
Similarly to Ca and Mg, Y is an effective element for controlling the
20 configurations of oxides and sulfides, and Y may be added according to necessity. In the
case where the content of Y is less than 0.001%, the effect cannot be obtained. In
addition, in the case where the content of Y exceeds 0.03%, the effect is saturated, and the
forgeability deteriorates. Therefore, the content of Y is set to be in a range of 0.001% to
0.03%.
25 [0053]
29
Zr: 0.001%to 0.03%
Similarly to Y, Ca, and Mg, Zr is an effective element for controlling the
configurations of oxides and sulfides, and Zr may be added according to necessity. In the
case where the content of Zr is less than 0.001%, the effect cannot be obtained. In
5 addition, in the case where the content of Zr exceeds 0.03%, the effect is saturated, and the
forgeability deteriorates. Therefore, the content of Zr is set to be in a range of 0.001% to
0.03%.
[0054]
La: 0.001% to 0.03%
10 Similarly to Zr, Y, Ca, and Mg, La is an effective element for controlling the
configurations of oxides and sulfides, and La may be added according to necessity. In
the case where the content of La is less than 0.001%, the effect cannot be obtained. In
addition, in the case where the content of La exceeds 0.03%, the effect is saturated, and
the forgeability deteriorates. Therefore, the content of La is set to be in a range of
15 0.001% to 0.03%.
[0055]
Ce: 0.0011° ata Q.03%_
Similarly to La, Zr, Y, Ca, and Mg, Cc is an effective element for controlling the
configurations of oxides and sulfides, and Ce may be added according to necessity. In
20 the case where the content of Cc is less than 0.001%, the effect cannot be obtained. In
addition, in the case where the content of Cc exceeds 0.03%, the effect is saturated, and
the forgeability deteriorates. Therefore, the content of Cc is set to be in a range of
0.001% to 0.03%.
[0056]
25 Other components will not be specifically defined; however, there are cases in
30
which elements of Sri, Sb, Zn, Zr, As, and the like incorporate from a scrap of a raw
material as inevitable impurities. However, the characteristics of the hot-rolled steel
plate are not greatly affected in the present embodiment at a level of the content at which
the above-described elements incorporate as impurities.
5 [0057]
(Plate thickness)
The plate thickness of the hot-rolled steel plate of the present embodiment is set
to be in a range of 2 mm to 25 mm in consideration of the configuration applied to plate
press forging. In the case where the plate thickness is less than 2 mm, it becomes
10 difficult to work (process) the steel plate in a thickening step or the like in plate forging;
and therefore, the steel plate becomes inferior in plate press forging properties. In the
case where the plate thickness exceeds 25 mm, a pressing load increases. In addition, it
becomes liable to impose limitations on a facility that is used for cooling control, coiling,
and the like in the production method of the present embodiment. Therefore, the upper
15 limit of the plate thickness is set to 25 mm.
[0058]
(Microstructure)
An area percentage of the pearlite bands is in a range of not more than the K
value represented by the following formula in a region of 4/l Ot to 6/l Ot when a plate
20 thickness is indicated by tin a cross section of a plate thickness that is parallel to a rolling
direction.
K value = 25.5 x C% + 4.5 x Mn%-6
In the case where the hot-rolled steel plate contains Cr, the area percentage of the
pearlite bands is not more than the K' value represented by the following formula instead
25 of "not more than the K value".
31
K'value=15x C% + 4.5 x Mn% + 3.2 x Cr% - 3.3
The pearlite band refers to an aggregate of pearlite phases having thicknesses of 5
μm or more in the plate thickness direction, and the aggregate is a band-shaped aggregate
in which the pearlite phases are arranged in the rolling direction at intervals of 20 μm or
5 less, and a length of the band-shaped aggregate in the rolling direction is in a range of 1
mm or longer.
FIG. 8 is a view showing a relationship between ratios of (the area percentage of
the pearlite bands) / (the K value or the K' value) and anisotropies (4c/4L) in ultimate
deformability. As shown in FIG. 8, it is found that, in the case where the ratio of (the
10 area percentage of the pearlite bands) / (the IC value or the K' value) is 1 or less, that is, in
the case where the area percentage of the pearlite bands is not more than the IC value or
not more than the IC' value, the anisotropy in ultimate deformability becomes 0.9 or more;
and therefore, the anisotropies in workability in the rolling direction and in the direction
perpendicular thereto can be reduced.
15 The area percentage of the pearlite bands is preferably in a range of 4.6% or less.
In this case, the anisotropy in ultimate deformability becomes 0.9 or more as shown in
FIGS. 3 and 4; and therefore;the-anisotropy in workability ca decreased reliably.
[0059]
[Method for producing the steel plate for cold forging according to the first
20 embodiment]
As described above, the steel plate for cold forging according to the first
embodiment is composed of the hot-rolled steel plate. The method for producing the
hot-rolled steel plate will be described below.
[0060]
32
The method for producing the hot-rolled steel plate includes: heating a slab;
subjecting the heated slab to rough rolling so as to make a rough bar, subjecting the rough
bar to finishing rolling so as to make a rolled material; after the finishing rolling,
subjecting the rolled material to air cooling; cooling the rolled material to a coiling
5 temperature; and coiling the cooled rolled material so as to make a hot-rolled steel plate.
[0061]
(Step of heating a slab).
A slab (continuously cast slab or steel ingot) having the above-described chemical
components of the present embodiment is directly inserted to a heating furnace, or the slab
10 is cooled once, and then the slab is inserted to the heating furnace. Thereafter, the slab is
heated at a temperature of 1150°C to 1300°C.
In the case where the heating temperature is lower than 1150°C, a rolling
temperature during hot rolling in the subsequent step lowers. Thereby, recrystallization
behaviors during rough rolling and recrystallization behaviors during air cooling after
15 continuous hot rolling do not progress; and as a result, extended grains remain, or
anisotropy in workability increases. Therefore, the lower limit of the heating
temperature is set to 1150°C-or higher. In-the-case where-the-heating-temperature
exceeds 1300°C, crystal grains coarsen during the heating; and thereby, anisotropy in
workability increases. Therefore, the heating temperature is in a range of 1150°C to
20 1300°C, and preferably in a range of 1150°C to 1250°C.
Meanwhile, the heated slab (continuously cast slab or steel ingot) is subjected to
the hot rolling in the subsequent step, and there is little difference in the characteristics of
the steel plate between the case in which the slab is directly inserted to the heating furnace
and the case in which the slab is cooled once and then inserted to the heating furnace. In
33
addition, the hot rolling in the subsequent step may be either one of ordinary hot rolling or
continuous hot rolling in which a rough bar is joined in finishing rolling, and there is little
difference in the characteristics of the steel plate.
[0062]
5 (Step of rough rolling)
Rough rolling includes a first rolling and a second rolling that is carried out`30
seconds or more after an end of the first rolling. The first rolling is carried out under
conditions where a temperature is in a range of 1020°C or higher and a sum of rolling
reduction rates is in a range of 50% or more. The second rolling is carried out under
10 conditions, where a temperature is in a range of 1020°C or higher and a sum of rolling
reduction rates is in a range of 15% to 30%.
The pearlite bands are generated due to segregation of alloy elements such Mn, P,
and the like. Therefore, it is effective to suppress uneven distribution of the alloy
elements (to reduce a proportion of uneven distribution of the alloy elements) in order to
15 reduce an area fraction (area percentage) of the pearlite bands. In the related art, as a
method for suppressing the uneven distribution of the alloy elements, a process was
carried-out-in which-the slab (M-Het)-was-heatedat a high temperature for long time
before hot rolling. In this process of the related art, the productivity degrades, and the
costs increase . Furthermore, the amount of energy consumption becomes significant, and
20 an increase in an amount of generated CO2 is caused.
The inventors paid attention to the fact that diffusion of the alloy elements is
promoted through work strains or grain boundary migration. Asa result, the inventors
found that the alloy elements are diffused by controlling conditions of the rough rolling as
follows; and thereby, the uneven distribution of the alloy elements can be suppressed.
25 [0063]
34
Firstly, the first rolling is carried out under conditions where a temperature is in a
range of 1020°C or higher and a sum of rolling reduction rates (total rolling reduction rate)
is in a range of 50%u or more. Thereby, dislocation density is increased, and in addition,
diffusion of the alloy elements is promoted due to grain boundary migration which is
5 caused by recrystallization of austenite. The upper limit of the temperature of the first
rolling is preferably 1200°C. In the case where the temperature exceeds 1200°C, the slab
becomes liable to be decarburized, which is not preferable. The sum of the rolling
reduction rates (total rolling reduction rate ) of the first rolling is preferably in a range of
60% or more, and more preferably in a range of 70% or more. The upper limit of the
10 sum of the rolling reduction rates (total rolling reduction rate) is preferably 90%. In the
case where the sum of the rolling reduction rates (total rolling reduction rate) exceeds 90%,
it becomes difficult to terminate the rolling at a temperature of 1020°C or higher, which is
not preferable.
Next, the second rolling is carried out at the time when 30 seconds or more pass
15 after the end of the first rolling. The second rolling is carried out under conditions where
a temperature is in a range of 1020°C or higher and a sum of the rolling reduction rates
(total rolling remotion rate) is in a rang l-5% to 30% There yam, recrystallized
austenite grains grow, and the alloy elements are pulled by migrating grain boundaries so
that the alloy elements diffuse. The elapsed time from the end of the first rolling to the
20 beginning of the second rolling is preferably in a range of 45 seconds or more, and more
preferably in a range of 60 seconds or more. The upper limit of the temperature of the
second rolling is preferably 1200°C. In the case where the temperature exceeds 1200°C,
the slab becomes liable to be decarburized, which is not preferable.
Meanwhile, the number of times that each of the first rolling and the second
35
rolling that is carried out is not particularly limited. The first rolling and the second
rolling may be carried out once respectively, or may be carried out two or more times
respectively, as long as the rolling temperatures, the sums of the rolling reduction rates
(total rolling reduction rates), and the elapsed time from the end of the first rolling to the
5 beginning of the second rolling are within the above-described ranges. In any of these
cases, the same effects can be obtained.
[0064]
(Step of finishing rolling)
The rough bar that is obtained through the rough rolling is subjected to finishing
10 rolling under a conditions where a finishing temperature is in a range of Ae3 or higher.
The Ae3 is a value calculated from the following formula.
Ae3 (°C) = 910 -372 x C% + 29.8 x Si% - 30.7 x Mn% + 776.7 x P% - 13.7 x
Cr% - 78.2Ni%
(Here, C%, Si%, Mn%, P%, Cr%, and Ni% represent the contents (% by mass) of
15 C, Si, Mn, P, Cr, and Ni included in the hot-rolled steel plate, respectively.)
In the case where the temperature of the finishing rolling (finishing temperature,
the end-temperature-of the finishing--rolling) islet to bein-a-r-angeof Ae3-or-higlier,
recrystallization is promoted . Generally, the Ae3 is used as a rough standard of the end
temperature of the finishing rolling. In the case where the end temperature of the
20 finishing rolling is Ae3 , the finishing rolling is terminated in a state of being austenite
structure . However, the austenite structure is in an overcooling state, and the
recrystallization does not occur sufficiently ; and as a result, an increase in anisotropy in
workability is promoted. Therefore, in the present embodiment, the finishing
temperature (the end temperature of the finishing rolling) is set to be in a range of Ae3 or
25 higher.
36
[0065]
(Step of air cooling)
After the finishing rolling, the rolled material is subjected to air cooling for 1
second to 10 seconds. In the case where the air-cooling time exceeds 10 seconds, the
5 temperature lowers greatly; and thereby, recrystallization behaviors progress at a slow rate.
Therefore, the effect of improving anisotropy in workability is saturated.
[0066]
(Step of cooling and coiling after air cooling)
After the air cooling, the rolled material is cooled to a coiling temperature of
10 400°C to 580°C at a cooling rate of 10°C/s to 70°C/s. In the case where the cooling rate
is less than 10°C/s, coarse ferrite and a coarse pearlite structure are formed. Therefore,
deformability degrades due to the coarse pearlite structure even when the above-described
hot rolling (the coarse rolling and the finishing rolling) is carried out. Therefore, the
lower limit of the cooling rate is set to 10°C/s or more. In addition, in the case where the
15 cooling rate exceeds 70°C/s, the steel plate is cooled unevenly in the width direction.
Particularly, potions at or in the vicinities of edges are cooled excessively; and thereby, the
portions are harden - Asa result, variation in quality of material is caul Therefore
it becomes necessary to add an additional step such as trimming of the edges; and thereby,
the yield is lowered. Therefore, the upper limit of the cooling rate is set to 70°C or less.
20 [0067]
Next, the cooled rolled material is coiled at a coiling temperature of 400°C to
580°C. In the case where the coiling temperature is lower than 400°C, martensite
transformation occurs in some portions of the steel plate, or the strength of the steel plate
increases. As a result, workability degrades. In addition, it becomes difficult to handle
37
the steel plate during uncoiling. On the other hand, in the case where the coiling
temperature exceeds 580°C, C (carbon) discharged during ferrite transformation
concentrates in austenite; and thereby, a coarse pearlite structure is generated. Since the
coarse pearlite structure promotes generation of pearlite bands, the area percentage of the
5 pearlite bands increases. As a result, deformability degrades, and anisotropy in
workability increases.
In the case where the coiling temperature is set to be in a range of 580°C or lower,
the structure is miniaturized, and generation of the coarse pearlite structure is suppressed.
As a result, degradation of deformability and an increase in anisotropy in workability can
10 be suppressed.
[0068]
(Second embodiment)
[Steel plate for cold forging according to the second embodiment]
Firstly, the configuration of the steel plate for cold forging according to the
15 second embodiment will be described with reference to FIG. 6. FIG. 6 is an explanatory
view schematically showing the steel plate for cold forging according to the second
-embodiment.
[0069]
As shown in FIG. 6, the steel plate for cold forging 1 according to the second
20 embodiment includes: a hot-rolled steel plate 10 which is a base material; and a
surface-treated film 100 formed on either one or both of main surfaces of the hot-rolled
steel plate 10.
[0070]
(Hot-rolled steel plate (a main body portion of the steel plate, a base material) 10)
25 The hot-rolled steel plate 10 which serves as the base material of the steel plate
38
for cold forging 1 is the hot-rolled steel plate as described in the first embodiment.
Therefore, detailed description of the hot-rolled steel plate 10 will not be made.
[0071]
(Surface-heated film 100)
5 The surface-treated film 100 has a concentration gradient of each component of
the film in a film thickness direction; and thereby, the film has a concentration-gradient
type three-layer structure in which three layers of an adhesion layer 110, a base layer 120,
and a lubricant layer 130 are identifiably situated in series from a side of an interface
between the surface-treated film 100 and the hot-rolled steel plate 10 towards a surface
10 side of the surface-treated film 100.
[0072]
Here, the "concentration-gradient type" in the present embodiment does not refer
to a fact that the respective layers of the adhesion layer 100, the base layer 120, and the
lubricant layer 130 which are included in the surface-treated film 100 are completely
15 separated and divided into three layers (the components of one layer are not present in
other layers), but means that, as described above, the components included in the
surface-treatedfilm 10 have concentration gradients in the film hickness_direc I ion. _ _
That is, main components in the surface-treated film 100 include a component originating
from a silanol bond (the details will be described below) formed between a metal in the
20 surface of the hot-rolled steel plate 10 which is the base material and the surface-treated
film, a high-temperature resin (heat-resistant resin), an inorganic acid salt, and a lubricant.
Each of the components has a concentration gradient in the film thickness direction of the
surface-treated film 100. In more detail, a concentration of the lubricant 131 increases,
and, conversely, concentrations of the high-temperature resin and the inorganic acid salt
25 decrease, from the side of the interface between the surface-treated film 100 and the
39
hot-rolled steel plate 10 toward the surface side of the surface-treated film 100. In
addition, a concentration of the component originating from the silanol bond increases
toward the vicinity of the interface between the surface-treated film 100 and the hot-rolled
steel plate 10.
5 [0073]
Hereinafter, configurations of the respective layers that constitute the
surface-treated film 100 will be described in detail.
[0074]

10 The adhesion layer 110 secures adhesion properties between the surface-treated
film 100 and the hot-rolled steel plate 10 which is the base material with respect to
working during cold forging; and thereby, the adhesion layer 110 has roles of preventing
seizure between the steel plate for cold forging l and a mold. Specifically, the adhesion
layer 110 is situated on a side of an interface between the surface-treated film 100 and the
15 hot-rolled steel plate 10, and the adhesion layer 110 is a layer that includes a largest
amount of the component originating from the silanol bond among the three layers that
compose the-surface-treated61m_LQO
[0075]
Here, the silanol bond in the present embodiment is represented by Si-O-X (X
20 represents a metal that is a component of the hot-rolled steel plate), and the silanol bond is
formed at or in the vicinity of the interface between the surface-treated film 100 and the
hot-rolled steel plate 10. The silanol bond is assumed to be a covalent bond between a
silane coupling agent included in a surface treatment fluid for forming the surface-treated
film 100 and an oxide of the metal in the surface of the hot-rolled steel plate 10 (the metal
25 is for example, a kind of metal (Zn, Al, or the like) used in plating in the case where the
40
hot-rolled steel plate 10 is subjected to plating, or Fe in the case where the hot-rolled steel
plate 10 is a non-plated steel plate). In addition, the presence of the silanol bond can be
confirmed by a method which is capable of conducting elemental analysis in a depth
direction of a test specimen. For example, spectrum intensities of component elements
5 (Si, 0, and X) originating from the silanol bond in a film thickness direction of the
surface-treated film 100 are measured by a high-frequency glow-discharge optical
emitting spectroscopic apparatus (high-frequency GDS), and then contents of the
respective elements are determined from the spectrum intensities. Thereby, the presence
of the silanol bond can be confirmed. In addition, the presence of the silanol bond can
10 also be confirmed through direct observation of a cross section of a test specimen using a
field emission transmission electron microscope (FE-TEM) or the like, or the presence of
the silanol bond can be confirmed through a microanalysis of elements (for example, an
analysis method by using an energy dispersive X-ray spectrometer (EDS)), or the like.
[0076]
15 In addition, a thickness of the adhesion layer 110 needs to be in a range of 0.1 nm
to 100 run. In the case where the thickness of the adhesion layer 110 is less than 0.1 rim,
the forramg_of the-silanol bond-is-not-sufficient; andnhereby, a-sufficient adhering}orce
between the surface-treated film 100 and the hot-rolled steel plate 10 cannot be obtained.
On the other hand, in the case where the thickness of the adhesion layer 110 exceeds 100
20 am, a number of the silanol bonds are excessively large; and thereby, internal stress in the
adhesion layer 110 increases during working of the steel plate for cold forging 1, and the
film becomes brittle. Therefore, the adhering force between the surface-treated film 100
and the hot-rolled steel plate 10 degrades. The thickness of the adhesion layer 110 is
preferably in a range of 0.5 nm to 50 nm from the viewpoint of securing the adhering
25 force between the surface-treated film 100 and the hot-rolled steel plate 10 more reliably.
41
[0077]

The base layer 120 has a role of improving the tracking of the steel plate
(followability) during cold forging. In addition, the base layer 120 holds the lubricant
5 131; and thereby, the base layer 120 has a role of supplying the steel plate for cold forging
1 with hardness and strength with respect to seizure between the steel plat and the mold.
Specifically, the base layer 120 is situated as an intermediate layer between the adhesion
layer 110 and the lubricant layer 130, and the base layer 120 includes largest amounts of
the high-temperature resin and the inorganic acid salt as main components among the
10 three layers that compose the surface-treated film 100: In detail, the base layer 120 has
the largest contents of the high-temperature resin and the inorganic acid salt included in
the whole layer among the three layers.
[0078]
A reason why the inorganic acid salt is selected as the component mainly
15 included in the base layer 120 is as follows. The inorganic acid salt can form a film of a
concentration-gradient type three-layer structure in the present embodiment, and the
inorganic acid saltis appropriate-for playing the aboie-described-role of the haselayer 129
Meanwhile, in the present embodiment, the surface-treated film 100 is formed using a
water-based surface treatment fluid. Therefore, the inorganic acid salt in the present
20 embodiment is preferably water-soluble in consideration of the stability of the surface
treatment fluid. However, even when a salt is insoluble or rarely soluble in water, the
salt can be used if soluble in an acid. For example, a film including zinc phosphate can
be formed by using a combination of a water-soluble inorganic acid salt (for example, zinc
nitrate), and an acid (for example, phosphate).
25 [0079]
42
In terms of the above-described roles, examples of the inorganic acid salt that can
be used in the present embodiment include phosphate, borate, silicate, molybdate,
tungstate, or combinations of a plurality of the above-described salts. Specifically,
examples of the inorganic acid salt that can be used include zinc phosphate, calcium
5 phosphate, sodium borate, potassium borate, ammonium borate, potassium silicate,
potassium molybdate, sodium molybdate, potassium tungstate, sodium tungstate, and the
like. However, among the above-described salts, the inorganic acid salt is particularly
preferably at least one kind of compound selected from a group consisting of phosphate,
borate, and silicate for reasons of expediency (convenience) when the thicknesses of the
10 respective layers of the adhesion layer 100, the base layer 120, and the lubricant layer 130
are measured,
[0080]
In addition, the base layer 120 includes the high-temperature resin as a main
component. As described above, during cold forging, the temperature becomes relatively
15 high due to the friction force between the steel plate for cold forging 1 which is a base
material and the mold. Therefore, a reason why the high-temperature resin is selected is
that the-surface-treated-film I00-needlstamaintain afilm shape e en under-working
conditions of such a high, temperature. From the above-described viewpoint, heat
resistance of the high-temperature resin in the present embodiment is preferably favorable
20 enough to hold a film shape at a temperature of higher than the achieving temperature
(approximately 200°C) during cold forging. Meanwhile, in the present embodiment, the
surface-treated film 100 is formed using a water-based surface treatment fluid. Therefore,
the high-temperature resin in the present embodiment is preferably water-soluble in
consideration of the stability of the surface treatment fluid.
25 [0081]
43
In terms of the above-described roles, examples of the high-temperature resin that
can be used in the present embodiment include a polyimide resin, a polyester resin, an
epoxy resin, a fluroresin, and the like. In particular, in order to secure sufficient heat
resistance and water solubility, a polyimide resin is preferably used as the
5 high-temperature resin.
[0082]
In addition, the composition of the base layer 120 also has an influence on the
entire composition of the steel plate for cold forging 1. Therefore, in the present
embodiment, the high-temperature resin is used as a main component of the base layer 120
10 in order to confer work tracking and heat resistance of the surface-treated film 100, and for
example, like Patent Document 4, an inorganic component such as phosphate, borate,
silicate, molybdate, tungstate, or the like is not used as a main component. Specifically,
an amount of the inorganic acid salt in the base layer 120 is in a range of 1 part by mass to
100 parts by mass with respect to 100 parts by mass of the high-temperature resin. In the
15 case where the amount of the inorganic acid salt is less than 1 part by mass, a friction
coefficient of the surface-treated film 100 increases; and thereby, sufficient lubricity
cannot be obtained. On the otheLhand,in the case-where the amount ofthe-ii organic
acid salt exceeds 100 parts by mass, performance for holding the lubricant 131 is not
sufficiently exhibited.
20 [0083]
In addition, a thickness of the base layer 120 needs to be in a range of 0.1 μm to
15 μm. In the case where the thickness of the base layer 120 is less than 0.1 μm, the
performance for holding the lubricant 131 is not sufficiently exhibited. On the other
hand, in the case where the thickness of the base layer 120 exceeds 15 μm, the film
25 thickness of the base layer 120 is excessively thick; and thereby, pressing scratch or the
44
like becomes liable to occur during working (cold forging). The thickness of the base
layer 120 is preferably in a range of 0.5 μm or more from the viewpoint of improving the
performance for holding the lubricant 131, and the thickness of the base layer 120 is
preferably in a range of 3 μm or less from the viewpoint of more reliably preventing the
5 pressing scratch during working.
[0084]

The lubricant layer 130 has a role of improving lubricity of the surface-treated
film 100 so as to reduce a friction coefficient. Specifically, the lubricant layer 130 is
10 situated on an outermost surface side of the surface-treated film 100, and the lubricant
layer 130 is a layer which includes a largest amount of the lubricant 131 among the three
layers that compose the surface-treated film 100.
[0085]
In the present embodiment, the lubricant 131 is not particularly limited as long as
15 the lubricant can form the surface-treated film 100 having a concentration-gradient type
three-layer structure and the lubricant sufficiently improves the lubricity of the
surface-treated frlrrri00. For example, it is possible-to-use at least-one kind selected
from a group consisting of polytetrafluoroethylene, molybdenum disulfide, tungsten
disulfide, zinc oxide, and graphite.
20 [0086]
In addition, a thickness of the lubricant layer 130 needs to be in a range of 0.1 μm
to 10 μm. In the case where the thickness of the lubricant layer 130 is less than 0.1 μm,
sufficient lubricity cannot be obtained. On the other hand, in the case where the
thickness of the lubricant layer 130 exceeds 10 μm, redundant unwanted material is
45
generated during working, and a disadvantage occurs in which the redundant unwanted
material attaches to the mold or the like. The thickness of the lubricant layer 130 is
preferably in a range of 1 μm or more from the viewpoint of further improving the
lubricity. In addition, the thickness of the lubricant layer 130 is preferably in a range of 6
5 μm or less from the viewpoint of more reliably preventing generation of the redundant
unwanted material during working.
[0087]
Furthermore, in order to play the roles of the base layer 120 and the lubricant
layer 130, a thickness ratio between the lubricant layer 130 and the base layer 120 is also
10 important. Specifically, a ratio of the thickness of the lubricant layer 130 to the thickness
of the base layer 120, that is, (the thickness of the lubricant layer) / (the thickness of the
base layer) needs to be in a range of 0.2 to 10. In the case where (the thickness of the
lubricant layer) / (the thickness of the base layer) is less than 0.2, the surface-treated film
100 is hardened excessively throughout the film; and thereby, the lubricity cannot be
15 sufficiently obtained. On the other hand, in the case where (the thickness of the lubricant
layer) / (the thickness of the base layer) exceeds 10, the holding properties of the lubricant
- 1-3-1--deteriorate-,and the-work tracki-nglaeks throughout he film.
[0088]

As described above, in the steel plate for cold forging 1 according to the present
embodiment, it is important that the adhesion layer 110 is present on the side of the
25 hot-rolled steel plate 10, the lubricant layer 130 is present on the film surface side, and the
46
base layer 120 is present therebetween. The lubricity that can tolerate cold forging,
which is intended in the present embodiment, cannot be exhibited if any one of the layers
is not present. In addition, even in the case where the thicknesses of the respective layers
of the adhesion layer 110, the base layer 120, and the lubricant layer 130 are not within the
5 above-described ranges, the lubricity that can tolerate cold forging, which is intended in
the present embodiment, cannot be exhibited. Therefore, in the present embodiment, a
method for confirming whether or not the respective layers of the adhesion layer 110, the
base layer 120, and the lubricant layer 130 are formed, and a method for measuring the
film thicknesses become important.
10 [0089]
Firstly, examples of the method for confirming whether or not the respective
layers of the adhesion layer 110, the base layer 120, and the lubricant layer 130 are formed
include a method in which quantitative analysis of elements are carried out in the film
thickness direction (depth direction) of the surface-treated film 100 using a high-frequency
15 GDS. That is, firstly, representative elements (characteristic elements in the components)
of the main components (the component originating from the silanol bond, the inorganic
acid salt4he high4emperaturereein,and the inAhe surface-Treated- film
100 are set. For example, with regard to the component originating from the silanol bond,
Si is set as`the representative element. With regard to the lubricant, appropriately, F is set
20 as the representative element in the case where the lubricant is polytetrafluoroethylene,
and Mo is set as the representative element in the case where the lubricant is molybdenum
disulfide. Next, intensities of peaks that correspond to these representative elements are
obtained in a measurement chart of the high-frequency GDS. Concentrations of the
respective components at each location in the film thickness direction can be calculated
25 from the obtained peak intensities.
47
[0090]
The method for measuring the thicknesses of the respective layers in the present
embodiment is defined as below. Firstly, a depth (a location in the film thickness
direction) of a portion having a peak intensity of half the maximum value of the peak
5 intensity of the representative element (for example, F, Mo, W, Zn, and C) of the lubricant,
which is set in the above-described manner, from the outermost surface of the
surface-treated film 100 in the measurement chart of the high-frequency GDS is
considered as the thickness of the lubricant layer 130. That is, the location in the film
thickness direction of the portion having a peak intensity of half the maximum value of the
10 peak intensity of the representative element of the lubricant serves as an interface between
the lubricant layer 130 and the base layer 120.
[0091]
In addition, a depth (a location in the film thickness direction) of a portion having
a peak intensity of half the maximum value of the peak intensity of the representative
15 element (Si) of the component originating from the silanol bond, from the interface
between the surface-treated film 100 and the hot-rolled steel plate 10 in the measurement
chart oLthehigh-freduency GDS is consideredasjhethickness _oFthe_adhesion layer 110.
That is, the location in the film thickness direction of the portion having a peak intensity
of half the maximum value of the peak intensity of the representative element (Si) of the
20 component originating from the silanol bond serves as an interface between the adhesion
layer 110 and the base layer 120.
[0092]
Furthermore, the thickness of the base layer 120 is defined as a depth from the
portion having a peak intensity of half the maximum value of the peak intensity of the
25 representative element of the lubricant to the portion having a peak intensity of half the
48
maximum value of the peak intensity of the representative element (Si) of the component
originating from the silanol bond. Meanwhile, for example, the thickness of the base
layer 120 may be obtained as follows. The thickness of the entire surface-treated film
100 is measured from a cross section of the surface-treated film 100 observed using a
5 microscope, and then a sum of the thickness of the adhesion layer 110 and the thickness of
the lubricant layer 130 which are obtained in the above-described manner is subtracted
from the thickness of the entire surface-treated film 100.
(0093]
However, in the case where graphite is used as the lubricant 131, when carbon
10 (C) is set as the representative element, it is difficult to differentiate the carbon from the C
element derived from the high-temperate resin and the like. Therefore, the thickness of
the lubricant layer 130 is measured using the representative element (for example, P, B, or
Si) of the inorganic acid salt component. Even in this case, the location in the film
thickness direction of a portion having a peak intensity of half the maximum value of the
15 peak intensity of the representative element of the inorganic acid salt component serves as
the interface between the lubricant layer 130 and the base layer 120.
[0924]
In addition, in the case where silicate is used as the inorganic acid salt of the base
layer 120, when silicon (Si) is set as the representative element, it is difficult to
20 differentiate Si derived from silicate as the inorganic acid salt from Si derived from the
component originating from the silanol bond in the adhesion layer 110. Therefore, the
thicknesses of the adhesion layer 110 and the base -layer 120 are measured using the
carbon (C) derived from the high-temperature resin component in the base layer 120 as the
representative element.
25 Furthermore, in the case where molybdate or tungstate is used as the inorganic
49
acid salt of the base layer 120, when molybdenum (Mo) or tungsten (W) is set as the
representative element, there are cases in which it is difficult to differentiate Mo or W
derived from the inorganic acid salt from Mo or W derived from the lubricant 131. In
this case, the thicknesses of the base layer 120 and the lubricant layer 130 are measured
5 using an element that the inorganic acid salt and the lubricant 131 do not have in common,
for example, sulfur (S) derived from the lubricant 131 as the representative element.
[0095]
Meanwhile, in the method for calculating the thicknesses of the respective layers,
the locations of the respective layers in the film thickness direction of the surface-treated
10 film 100 can be obtained from the locations of the portions having the peak intensities of
half the maximum values of the peak intensities of the representative elements of the
respective components, that is, sputtering times (in the case of the present embodiment,
times converted into the sputtering rate of Si02) by the high-frequency (.JDS in the
above-described manner.
15 [0096]
The amounts of the high-temperature resin and the inorganic acid salt in the base
layer are measured byihe following method--The-surface-treated film is cutic the
thickness direction using a microtome or the like, and the base layer is cut out. A test
specimen having an amount necessary for analysis is taken from the base layer, and the
20 test specimen is crushed using an agate mortar. An initial weight of the test specimen for
analysis is measured, and then, a solution that dissolves the inorganic acid salt, such as
water, is added; and thereby, the inorganic acid salt is dissolved. The inorganic acid salt
is dissolved, and then the test specimen for analysis is sufficiently dried. A weight of the
dried test specimen for analysis is used as a mass (parts by mass) of the high-temperature
25 resin, and a difference in the weight between the initial weight and the weight after drying
50
is used as a mass (parts by mass) of the inorganic acid salt. Thereafter, the amount (parts
by mass) of the inorganic acid salt with respect to the 100 parts by mass of the
high-temperature resin 100 is calculated from the calculated amounts of the
high-temperature resin and the inorganic acid salt in the base layer.
5 [0097]
[A method for producing the steel plate for cold forging according to the second
embodiment]
Thus far, the configuration of the steel plate for cold forging according to the
second embodiment has been described in detail, and subsequently, a method for
10 producing the steel plate for cold forging according to the second embodiment having the
above-described configuration will be described.
[0098]
The method for producing the steel plate for cold forging according to the second
embodiment includes: obtaining a hot-rolled steel plate 10 by the method for producing
15 the hot-rolled steel plate of the first embodiment; and forming a surface-treated film 100
on either one or both of main surfaces (a front surface and a rear surface) of the hot-rolled
steel plate-M.-
Since the step of obtaining the hot-rolled steel plate is the same as that in the first
embodiment, explanation thereof will not be made.
20 The step of forming the surface-treated films 100 includes: coating a water-based
surface treatment fluid including a water-soluble silane coupling agent, a water-soluble
inorganic acid salt, a water-soluble high-temperature resin, and a lubricant on either one or
both of the main surfaces of the hot-rolled steel plate 10 so as to form a coated film; and
drying the coated film so as to form the surface-treated film 100 on either one or both of
25 the main surfaces of the hot-rolled steel plate 10.
51
[0099]
(Regarding the surface treatment fluid)
The surface treated fluid that is used in the method for producing the steel plate
for cold forging according to the present embodiment includes a water-soluble silane
5 coupling agent, a water-soluble inorganic acid salt, a water-soluble high-temperature resin,
and a lubricant. The details of the inorganic acid salt, the high-temperature resin, and the
lubricant have been described, and thus explanation thereof will not be made.
[0100]
The water-soluble silanc coupling agent is not particularly limited, and a
10 well-known silane coupling agent can be used. Examples thereof that can be used
include 3-aminopropyltrimethoxy silane,
N-2-(aminomethyl)-3-aminopropylmethyldimethoxy silane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.
[0101]
15 In addition, a variety of additives may be added to the surface treatment fluid.
[0102]
Thesurface-treaturentlluid_that is used in the method-for-producing Ibc steel plate
for cold forging according to the present embodiment may contain a leveling agent for
improving coating properties, a water-soluble solvent, a metal stabilizer, an etching
20 suppressor, a pH adjuster, and the like at amounts within ranges in which the effects of the
present embodiment are not impaired. Examples of the leveling agent include nonionic
surfactants and cationic surfactants, and specifically, examples thereof that can be used
include adducts of polyethylene oxides or polypropylene oxides, acetylene glycol
compounds, and the like. Examples of the water-soluble solvent include: alcohols such
25 as ethanol, isopropyl alcohol, t-butyl alcohol, and propylene glycol; cellosolves such as
52
ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether; esters such as ethyl
acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl
ketone, and the like. Examples of the metal stabilizer include chelate compounds such as
EDTA, DTPA, and the like. Examples of the etching suppressor include amine
5 compounds such as ethylene diamine, triethylene pentamine, guanidine, pyridine, and the
like. Particularly, compounds having two or more amino groups in a single molecule
also have the effects of the metal stabilizer; and therefore, such compounds are more
preferable. Examples of the pH adjuster include: organic acids such as acetic acid, and
lactic acid; inorganic acids such as hydrofluoric acid; ammonium salts; amines, and the
10 like.
[0103]
The surface treatment fluid that is used in the method for producing the steel plate
for cold forging according to the present embodiment can be prepared by evenly
dissolving or dispersing the respective components in water.
15 [0104]
(Coating and drying of the surface treated fluid)
Examplesm£the methadfor coating the-surfacetreatment fluid on the hot rotled
steel plate 10 include a method in which the hot-rolled steel plate 10 is immersed in the
surface treatment fluid. In this case, it is necessary to heat the hot-rolled steel plate 10 to
20 a temperature higher than a temperature of the surface treatment fluid in advance, or in the
alternative, it is necessary to dry the hot-rolled steel plate using warm air during drying.
Specifically, the hot-rolled steel plate 10 is immersed in warm water at approximately
80°C for approximately one minute, and then, the hot-rolled steel plate 10 is immersed in
the surface treatment fluid at a temperature of approximately 40°C to 60°C for
25 approximately one second. Thereafter, the hot-rolled steel plate is dried at room
53
temperature for approximately 2 minutes. Thereby, the concentration-gradient type
surface-treated film 100 having a three-layer structure composed of the adhesion layer 110,
the base layer 120, and the lubricant layer 130 can be formed.
[0105]
5 (Method for controlling the film thicknesses of the respective layers)
The coated amount of the surface treatment fluid, the concentrations of the
respective components in the surface treatment fluid, and reactivities and hydrophilicities /
hydrophobicities of the surface treatment fluid and the hot-rolled steel plate 10 which is
the base material are appropriately controlled. Thereby, the film thicknesses of the
10 respective layers that compose the surface-treated film 100 can be adjusted to be within
the above-described ranges of the film thicknesses.
[0106]
(Reasons why the concentration-gradient type film is formed)
As described above, the surface treatment fluid in which the water-soluble silane
15 coupling agent, the water-soluble inorganic acid salt, the water-soluble high-temperature
resin, and the lubricant are dissolved or dispersed in water is coated on the hot-rolled steel
^1ate10,and-then dried. Thereby, the concentration-gradient typesurface-trcaLcdfilm
100 is formed. The inventors assumed that reasons why the concentration-gradient type
surface-treated film 100 is formed are as follows.
20 Firstly, in the case where the hot-rolled steel plate 10 is heated to a temperature
higher than the temperature of the surface treatment fluid in advance as described above,
the temperature of the hot-rolled steel plate 10 is higher than the temperature of the
surface treatment fluid. Therefore, in the coated film (thin film) formed by coating the
surface treatment fluid on the hot-rolled steel plate 10, temperature of a solid-liquid
25 interface is high; however, temperature of a gas-liquid interface becomes low. As a
54
result, a difference in temperature occurs in the coated film (thin film); and thereby, water
which serves as the solvent is volatilized such that fine convection occurs in the coated
film (thin film).
In addition, in the case where the surface treatment fluid at room temperature is
5 coated on the hot-rolled steel plate 10 at room temperature so as to form the coated film
(thin film), and then the hot-rolled steel plate is dried using warm air, temperature of a
gas-liquid interface becomes high, and a surface tension at the gas-liquid interface
becomes low. Fine convection occurs in the coated film (thin film) in order to alleviate
the above-described phenomenon.
10 In any of these coating and drying methods, convection occurs, and a component
having a high affinity to air (for example, the lubricant) and components having high
affinities to metal and water (for example, the inorganic acid salt and the high-temperature
resin) are separated. Then, when water is gradually volatilized to form a film shape, a
concentration-gradient type film having concentration gradients of the respective
15 components is formed.
[0107]
Inaddition, in the present embodiment, since the_silane coupling agent has a high
affinity to metal in the surface of the hot-rolled steel plate 10, the silane coupling agent
diffuses to -the vicinity of the hot-rolled steel plate 10 in the coated film (thin film). Then,
20 it is considered that the silane coupling agent that reaches the vicinity of the hot-rolled
steel plate 10 forms a covalent bond with a metal oxide present in the surface of the
hot-rolled steel plate 10 (for example, zinc oxide in the case where the hot-rolled steel
plate 10 is subjected to zinc plating); and thereby, the silanol bond represented by Si-O-M
is formed. As such, the silanol bond is formed at or in the vicinity of the hot-rolled steel
25 plate 10; and thereby, adhesion between the surface-treated film 100 and the hot-rolled
55
steel plate 10 is extremely improved. Therefore, occurrence of seizure and galling is
prevented.
[0108]
The steel plate for cold forging according to the second embodiment as described
5 above can be produced by a method which is composed of simple treatment steps and is
preferable from the viewpoint of global environmental protection, and the steel plate for
cold forging has excellent lubricity. Therefore, due to the recent environmental measures,
cold forging is more commonly carried out rather than workings that involve large shape
deformation, such as hot forging accompanied by large energy consumption and cutting
10 work that causes a large amount of material loss. Even in the case where stricter plastic
working or complicate working is demanded, the steel plate for cold forging can be
worked without occurrence of seizure and galling between the steel plate and a mold or
other problems.
[0109]
15 Thus far, preferable embodiments of the present invention have been described in
detail with reference to the accompanying drawings; however, the present invention is not
--limited-to suckexamples. Itisevident that aperson-having 9rdinarylsnowledge in-the --
-technical field to which the invention belongs can imagine a variety of modified examples
and corrected examples within the scope of technical requirements as stated in the claims,
20 and it is needless to say that such examples are considered to be in the technical scope of
the present invention.
EXAMPLES
[0110]
Next, examples of the embodiments will be described; however, conditions in the
25 examples are one example of conditions which are employed to confirm the feasibility and
56
effects of the embodiments, and the embodiments are not limited to the example of
conditions. The embodiments can employ a variety of conditions within the features of
the embodiments as long as the objects of the embodiments are achieved.
[0111]
5 (Example 1)
50 kg of a steel ingot having the component composition as shown in Table 1 was
melted in a laboratory through vacuum melting, and a hot-rolled steel plate having a
thickness of 10 mm was produced under conditions that fulfilled the requirements as
described in the first embodiment. A cross-sectional portion of a plate thickness in
10 parallel with a rolling direction was taken from the hot-rolled steel plate. The
cross-sectional portion was subjected to a polishing treatment , and then the cross-sectional
portion was immersed in a Nital solution (a solution including approximately 5% of nitric
acid with the remainder being alcohol) ; and thereby, pearlite emerged. Next, with regard
to a central portion of the plate thickness in a region of 4/l Or to 6/l Or with respect to the
15 plate thickness t, the structure was photographed using an optical microscope (at a 50-fold
magnification, at a 100-fold magnification, and at a 200-fold magnification). The photos
ofthe observed structure are-shown in FIIG . 5Ato 5C.
[0112]
Table 1
20
Coiling
C Si Mn P S Al Cr Nb Ti N temperature
°C)
0.16 0.18 1.42 0.014 0.003 0.0032 0.03 0.04 0.001 0.0038 575
[0113]
From FIGS. SA to 5C, pearlite bands having lengths of 1 mm or more could be
confirmed. In the structure photo at a 100-fold magnification of FIG. 513, the pearlite
57
bands appear to be connected to each other without interspaces (intervals). In contrast, in
the structure photo at a 200-fold magnification of FIG. SC, interspaces (intervals) can be
confirmed in the pearlite bands, and some of the pearlite bands appear to be separated.
Generally, pearlite phases exist at grain boundaries of ferrite phases. In the examples, the
5 pearlite band was defined as an aggregate of the pearlite phases scattered in the grain
boundaries of the ferrite phases. In detail, the thicknesses of the respective pearlite
phases that configured the aggregate in a plate thickness direction were in a range of 5 μm
or more. The pearlite band was a band-shaped aggregate in which the pearlite phases
were arranged in a rolling direction at intervals of 20 μm or less, and a length of the
10 band-shaped aggregate in the rolling direction was in a range of 1 mm or longer.
An area percentage of the pearlite bands was measured by the following method.
The structure photos photographed at a 100-fold magnification were connected with each
other so as to make one piece of a structure image. Then, the structure image was
subjected to image analysis using an image analysis software (WinROOF Ver. 5.5.0
15 manufactured by Mitani Corporation); and thereby, the area percentage of the recognized
pearlite bands was measured.
[0114]
(Example 2)
50.-kg of a steel ingot having each of the component compositions as shown in
20 Tables 2 to 5 was melted in the laboratory through vacuum melting, and a steel plate
having a thickness of 10 mm was produced under each of the conditions as shown in
Tables 6 to 8. Meanwhile; the chemical compositions of the test specimens in Tables 6 to
8 are the same as the chemical compositions of steel ingots having the same steel numbers
as the test specimen numbers.
25 Samples for structure observation and round bar tension test specimens for
58
ultimate deformability measurement were taken from the obtained steel plates.
[0115]
An area fraction of pearlite bands having lengths of 1 mm or longer that were
present in a region of 4/l Ot to 6/l Ot was measured by the method as determined in
5 Example 1.
[0116]
A round bar tension test specimen having a diameter of 8 mm was taken along a
rolling direction from a central portion of the hot-rolled steel plate. Similarly, a round
bar tension test specimen having a diameter of 8 mm was taken along a direction
10 perpendicular to the rolling direction. Tension tests were carried out on the test
specimens. Areas of broken portions after breakage were measured, and ultimate
deformabilities were calculated from cross section shrinkage rates of the test specimens
after the tests according to the formula of the ultimate deformability. When the ultimate
deformability in the rolling direction was represented by ^L, and the ultimate deformation
15 in the direction perpendicular to the rolling direction was represented by ^c, a ratio
(4e/4L) was calculated. The area fractions of the pearlite bands and the ultimate
deformability ratios-which were obtain are-shown in Tables 9 and-t0.
Meanwhile, underlined numeric values in the tables indicate that they fail to meet
the requirements as defined in the embodiments.
20 [0117]
Table 2
Steel Components (% by mass) Ae3 K'
No C Si Mn P Al N 0 Cr B Others (°C)
A value
value
Note
1-1 0.13 0.14 0.53 0.01 0.0009 0.024 0.0033 0.0022 0.35 0.0012 850 0.0039 2.16 Invention steel
1-2 0.16 0.08 0.65 0.01 0.0006 0.02!,6 0.0027 0.0026 0.35 0.0016 839 0.0041 3.15 Invention steel
1-3 0.18 0.19 0.35 0.02 0.0015 0.031 0.0022 0.0028 0.68 0.0022 Nb:0.028 846 0.0053 3.15 invention steel
1-4 0.17 0.2 0.45 0.01 0.0008 0.029 0.0045 0.0017 0.45 0.0031 Ti:0.037 841 0.0035 2.72 Invention steel
1-5 0.13 0.22 0.65 0.01 0.0013 0.043 0.0032 0.0023 0.39 0.0026 V:0.018 853 0.0050 2.82 Invention steel
1-6 0.18 0.18 0.15 0.01 0.0025 0.02 1 0.0027 0.0021 0.82 0.0018
Nb:0.014,
843 0.0053 2.70 Ta:0.032 Invention steel
1-7 0.15 0.15 0.18 0.03 0.0011 0.026 0.0046 0.0014 1.27 0.0028 Nb:0.032 857 0.0034 3.82 invention steel
Nb:0.042,
1-8 0.14 0.55 0.48 0.01 0.0025 0.018 0.0034 0.0018 0.46 0.0022 Ti:0.013, 863 0.0049 2.43 Invention steel
W:0.052
1-9 0.15 0.07 0.65 0.01 0.0032 0.0316 0.0025 0.0021 0.43 0.0014 Ni:0.028 835 0.0065 3.25 Invention steel
1-10 0.14 0.16 0.21 0.01 0.0006 0.038 0.0028 0.0028 0.77 0.0009
Cu:0.04,
Mo:0.011 856 0.0047 121 Invention steel
1-11 0.17 0.25 0.48 0.02 0.0022 0.045 0.0031 0.0016 0.33 0.0015
Nb:0.023,
848 0.0053 2 47 Invention steel Cu:0.025
.
Nb:0.051,
1-12 0.2 0.18 0.65 0.02 0.0029 0.023 0.0036 0.0025 0.38 0.0013
Ti:0.007,
832 0.0062 3 84 Invention steel Ni:0.015, .
Mo:0.035
1-13 0.14 0.14 0.22 0.01 0.0022 0.029 0.0033 0.0024 0.45 0.0025 Mg:0.0015 856 0.0056 1.23 Invention steel
[0118]
Table 3
Steel Components (% by mass) Ae3 K'
No. C Si Mn P S kM N 0 Cr B Others (CC) A value
value
Note
1-14 0.15 0.35 0.86 0.03 0.0018 0.031 0.0041 0.0025 0.25 0.0029 Ca:0.0023 857 0.0053 3.62
Invention
steel
Nb:0.031,
1-15 0.17 0.22 0.48 0.01 0.0007 01022 0.0028 0.0019 0.66 0.0044 Ca:0.0028, 840 0.0033 3.52
Invention
La:0.005 steel
Nb:0.018,
1-16 0.18 0.19 0.25 0.02 0.0043 0 035 0.0031 0.0014 0.55 0.0021 Ti:0.021, 851 0.0069 2.29
4 Invention
Y:0.0088 steel
1-17 0.16 0.2 0.29 0.02 0.0025 0.026 0.0026 0.0027 0.83 0.0017
Ni:0.089,
842 0.0061 3 06
Invention
Zr:0.0092 . steel
Cu:0.034,
1-18 0.13 0.17 0.65 0.01 0.0018 0.017 0.0045 0.0022 0.38 0.0028 Mo:0.021, 849 0.0046 2.79 Invention
Ce:0.008
steel
Nb:0.031,
Ti:0.009,
1-19 0.15 0.05 0.56 0.02 0.0027 0.053 0.0036 0.0018 0.45 0.0014
Ni:0.015,
847 0.0062 2.91
Invention
Ca:0.0027, steel
La:0.003,
Ce:0.0062
[0119]
Table 4
Steel Components (% by mass)
I Ae3 K'
No. C Si Mn P S Ai N 0 Cr B Others (°C)
A value
value
Note
Ni:0.045,
Mo:0.022,
1-20 0.2 0.23 0.68 0.01 0.0019 0.017 0.0031 0.0025 0.31 0.0013 Ca:0.0021, 820 0.0050 3.75
Invention
La:0.004; steel
Ce:0.0085
Nb:0.038,
Ti:0.017,
V:0.011,
1-21 0.18 0.14 0.75 0.02 0.0022 0.063 0.0029 0.0023 0.23 0.0029
Mg:0.0028,
840 0 0066 3 51
Invention
Y:0.018,
. .
steel
Zr:0.004,
La:0.0035,
Ce:0.0073
1-22 0.16 0.06 0.88 0.02 0.0087 0.025 0.0023 0.0023 0.45 0.0014
Y:0.02,
837 0.0118 4.50
Comparative
Ce:0.012 steel
1-23 0.19 0.19 0.85 0.03 0.0092 0.01 0.0044 0.0046 0.38 0.0018 Ni:0.022 831 0.0148 4.59
Comparative
steel
1-24 0.17 0.25 0.87 0.02 0.0023 0.12 0.0038 0.0038 0.49 0.0022 Nb:0.028 836 0.0101 4.73
Comparative
steel
[0120]
Table 5
Steel Compo ents (% by mass) Ae3 K'
No. C Si Mn P S Al N 0 Cr B Others (°C)
A value
value
Note
Mo:0.035,
1-25 0.14 0.22 0.79 0.02 0.0041 0.039 0.0058 0.0028 0.38 0.0027 Ca:0.0018 848 0.0082 3.57 Comparative
, Y:0.026 steel
Nb:0.032,
Ti:0.016,
1-26 0.16 0.04 0.84 0.02 0.0025 0.029 0.0029 0.0048 0.45 0.0011 Ni:0.031, 834 0.0083 4.32
Comparative
La:0.0028,
steel
Ce:0.0091
1-27 0.17 0.18 2.51 0.02 0.0033 0.034 0.0031 0.0019 0.15 0.0006
Cu:0.026,
785 0.0063 11.03
Comparative
Mo:0.139 steel
Nb:0.029,
1-28 0.25 0.15 0.65 0.03 0.0029 0. 38 0.0042 0.0022 0.54 0.0012 Ni:0.017, 815 0.0064 5.10 Comparative
Cu:0.022 steel
[0121]
Table 6
Hot oiling conditions
n
N
>
(D
^o
rn

M'
N
h7
0 4 0
'D
,.^
o
w o
o o
°°
N
C)
o o H
tj ao as
y Q
o N
o r17
$ a
o rn
G ,'
o •s n
aq'^
h
- CD
o ° ao
n
ul^ 0
v ^C
?
s
r'Y
CC
^ vo
CD
ao 2,
1 1-h
N
.^ O
v
C]
o o
S'
^
o. W
v
CD
o
^ oa
0 rn
n
K
C -
1-lA 850 1220 1135 74 50.4 1027 27 855 1.5 18 530 Invention example
1-18 850 1200 1156 55 38.2 1116 25 870 1 18 510 Invention example
1-2A 839 1200 1136 69 60.4 1030 25 865 2 25 480 Invention example
1-2B 839 1120 1085 62 40 1051 21 850 2 38 550 Comparative example
1-3A 846 1180 1076 63 35.6 1031 22 875 5 38 580 Invention example
1-3B 846 1160 1050 58 38.7 1002 22 880 5 45 500 Comparative example
1-4A 841 1160 1097 61 41.9 1036 23 876 7 45 450 Invention example
1-413 841 1160 1010 57 32.9 982 23 846 6 30 460 Comparative example
1-5A 853 1220 1130 55 36.4 1080 26 910 9 45 475 Invention example
1-513 853 1150 1055 62 38.1 1038 18 880 8 30 550 Invention example
1-6A 843 1200 1098 58 35.4 1043 19 875 2 25 430 Invention example
1-6B 843 1200 1131 55 63.6 1039 8 891 5 30 480 Comparative example
1-7A 857 1180 1122 60 57.7 1040 26 875 3 30 450 Invention example
1-7B 857 1180 1148 66 23.7 1117 22 962 5 30 480 Comparative example
1-8A 863 1230 1118 58 38.1 1090 22 878 5 20 480 Invention example
1-8B 863 1150 1096 63 34.9 1047 28 798 8 35 500 Comparative example
1-9A 835 1180 1109 56 40.4 1061 27 873 2 15 550 Invention example
1-9B 835 1150 1051 66 41.6 1034 18 865 0.5 10 500 Comparative example
[0122]
Table 7
Hot rolling conditions
co
y •^-+
4
O c]
W
o
n
o
O
^?.
r
r^
0
to
`^ M O.
Cl
aq ,^
O
m o
h i=
'1]
U^Q
Oq m N
O
o o H
'-: ~
^CPyD
^.y
^' O O C'a o
n {^
O
o m
"3 y O.
O !ma y
UC i-J
O+ `6
O a
r
o ,^ 7^
OQ .^-i- =
Q^
O .3
2
O O G
n .i.
Y
`-+ '^"S
N
r
F h
o
vii !^( 7
n G.
'^ h
II. UQ O
v O
--.
UQ or,
o, o
^'
a
C7 "
O
('1
^.
`^
^^
v
tN
.
N
1-10A 856 1150 1093 60 37.5 1061 26 870 5 25 480 Invention example
1-lOB 856 1150 1002 59 48.2 978 27 868 6 15 470 Comparative example
1-1IA 848 1180 1066 59 37.4 1030 21 880 5 40 450 Invention example
1-11B 848 1220 1137 63 41 1089 20 865 4 5 520 Comparative example
1-11C 848 1220 1092 68 39.6 1026 16 876 5 40 630 Comparative example
1-12A 832 1230 1193 64 57.5 1114 18 915 8 55 550 Invention example
I-12B 832 1200 1079 67 34.1 1053 16 875 5 40 530 Invent on example
1-12C 832 1180 1135 57 58.4 1064 20 855 2.5 15 650 Comparative example
1-13A 856 1220 1144 55 46.3 1070 21 890 3.5 30 450 Invention example
1-13B 856 1180 1139 57 62.4 1066 26 875 6 15 480 Invention example
1-14A 857 1180 1064 58 37.6 1033 24 873 6 20 550 Invention example
1-14B 857 1180 1149 39 44.3 1040 22 891 6 30 520 Com arative example
1-15 840 1220 1165 61 66.9 1074 19 905 9 55 530 Invention example
1-16 851 1200 1107 57 47.3 1039 18 875 2 15 530 Invention example
1-17A 842 1200 1147 59 50.6 1074 25 870 3.5 30 520 Invention example
1-17B 842 1150 1049 60 41.4 1022 26 855 4 25 500 Invention example
1-17C 842 1200 1125 64 51.9 1042 18 805 6 10 610 Comparative example
1-18A 849 1180 1060 64 37.3 1031 23 870 7 35 480° Invention example
1-18B 849 1150 1073 58 37.5 1038 19 865 6 45 480 Invention example
[0123]
Table 8
Hot rolling conditions
co rn o
0 0 o to o

o.
O ` •
w^ °
N
o
(D ^ rn
=
(D
o o w °4 °Q rn
ri M a o o. n " o F ^Q rn
r
co o ry .3 ° N o .3 .. o CJ ... ° m a
1-19A 847 1220 1162 62 43.8 1119 27 870 8 40 550 Invention example
1-19B 847 1200 1127 66 63.5 1037 27 880 9 55 580 Invention example
1-20 820 1180 1075 64 35.9 1054 23 900 2 10 520 Invention example
1-21A 840 1230 1149 59 41.5 1124 25 915 7 30 500 Invention example
1-21B 840 1180 1131 61 35.3 1082 24 868 5 15 530 Invention example
1-21C 840 1170 1091 60 45.4 1026 19 870 0.5 15 550 Comparative example
1-22A 837 1180 1137 62 37.5 1096 24 877 2 15 530 Comparative example
1-22B 837 1180 1097 57 39.7 1046 28 855 1 15 550 Comparative example
1-23 831 1180 1131 60 36.2 1077 18 860 2 20 550 Comparative example
1-24 836 1180 1078 58 37.2 1048 18 880 4 25 530 Comparative example
1-25 848 1160 1108 58 57.4 1037 24 875 2 25 550 Comparative example
1-26 834 1160 1078 66 41.2 1036 18 860 2 25 530, Comparative example
1-27 785 1150 1084 61 37.4 1049 29 840 2 10 550 Comparative example
1-28 815 1150 1071 58 35.8 1044 25 865 2.5 20-580 Comparative example
66
[0124]
Table 9
Characteristics
of hot-rolled steel plate
Test
specimen
No.
A value K' value
Area fraction of
pearlite bands
having lengths of
1 nun or longer
Ultimate
deformability
/AA
ratio
Note
1-lA 0.0039 2.16 2 0.91 Invention example
1-IB 0.0039 2.16 1.9 0.93 Invention example
1-2A 0.0041 3.15 1.4 0.96 Invention example
1-2B 0.0041 3.15 5.2 0.75 Comparative example
1-3A 0.0053 3.15 3 0.91 Invention example
1-3B 3.15 5.9 0.74 Comparative example
1-4A 2.72 2 0.92 Invention example
1-4B q003 2.72 3.2 0.75 Comparative example
1-5A 2.82 1.55 0.94 Invention example
1-5B 2.82 1.2 0.96 Invention example
1-6A 0.0053 2.70 2.6 0.93 Invention example
1-6B 0.0053 2.70 2.9 0.78 Comparative example
1-7A 0.0034 3.82 1.9 0.98 Invention example
1-7B 0.0034 3.82 4.1 0.77 Comparative example
1-8A 0.0049 2.43 1.3 0.93 Invention example
1-8B 0.0049 2.43 3.8 0.77 Comparative example
1-9A 0.0065 3.25 1.2 0.96 Invention example
1-9B 0.0065 3.25 4.3 0.77 Comparative example
1-0A 0.0047 2.2-1 L4 -0:96 Invention example--
1-lOB 0.0047 2.21 2.8 0.72 Comparative example
MIA 0.0053 2.47 1.8 0.94 Invention example
1-11B - 0.0053 2.47 3.8 0.76 Comparative example
1-I1C 0.0053 2.47 4.8 0.73 Comparative example
1-12A 0.0062 3.84 2.3 0.94 Invention example
1-12B 0.0062 3.84 2.5 0.92 Invention example
1-12C 0.0062 3.84 4.5 0.72 Comparative example
[0125]
67
Table 10
Characteristics
of bot-rolled steel plate
Test
specimen
No.
A value K' value
Area. fraction of
pearlite bands
having lengths of
1 mm or longer
(%)
Ultimate
deformability
ratio
Note
1-13A 0.0056 1.23 0.8 0.93 Invention example
1-13B 0.0056 1.23 0.9 0.94 Invention example
1-14A 0.0053 3.62 2.4 0.92 Invention example
1-14B 0.0053 3.62 4.3 0.71 Comparative example
1-15 0.0033 3.52 2.1 0.93 Invention example
1-16 0.0069 2.29 1.5 0.91 Invention example
1-17A 0.0061 3.06 2.1 0.93 Invention example
1-17B 0.0061 3.06 2.1 0.94 Invention example
1-17C 0.0061 3.06 3.9 0.8 Comparative example
1-18A 0.0046 2.79 1.1 0.96 Invention example
1-18B 0.0046 2.79 1.2 0.94 Invention example
1-19A 0.0062 2.91 1.5 0.91 Invention example
1-19B 0.0062 2.91 1.4 0.93 Invention example
1-20 0.005 3.75 2.4 0.92. Invention example
1-21A 0.0066 3.51 2.7 0.94 Invention example
1-21B 0.0066 3.51 2.9 0.91 Invention example
1-21C 0.0066 3.51 4.8 0.76 Comparative example
1-22A 0.0118 4.50 3.3 0.7 Comparative example
1-22B -o-0118 -4.50- -- -3.8 0.65- Comparative example
1-23 0.0148 4.59 3.8 0.67 Comparative example
1-24 0.0101 4.73 3.5 0.73 Comparative example
1-25 10.0082 3.57 2.2 0.75 Comparative example
1-26 0.0083 4.32 3.1 0.72 Comparative example
1-27 0.0063 11.03 12.1 0.68 Comparative example
1-28 0.0064 5.10 6.3 0.8 Comparative example
[0126]
(Example 3)
5 501 cg of a steel ingot having each of the component compositions as shown in
Tables 11 and 12 was melted in the laboratory through vacuum melting, and a steel plate
68
having a thickness of 10 mm was produced under each of the conditions as shown in
Tables 13 to 15. Meanwhile, the chemical compositions of the test specimens in tables
13 to 15 are the same as the chemical compositions of steel ingots having the same steel
numbers as the test specimen numbers.
5 The area fractions of the pearlite bands and ultimate deformability ratios were
measured by the same methods as in Example 2. The obtained results are shown in
Tables 16 and 17.
[0127]
Table 11
Steel Compo ents (% by mass) Ae3 A K
No. C Si Mn P S Al N 0 Others (°C) value value
Note
2-1 0.14 0.02 1.25 0.005 0.0014 10.033 0.0024 0.0027 824 0.0052 3.20 Invention steel
2-2 0.15 0.13 1.34 0.009 0.0008 0.023 0.0025 0.0029 824 0.0045 3.86 Invention steel
2-3 0.16 0.15 1.28 0.02 0.0015 0.042 0.0031 0.0026 Nb:0.015 831 0.0055 3.84 Invention steel
2-4 0.13 0.04 1.85 0.018 0.0008 0.026 0.0029 0.0027 Ti:0.037 820 0.0044 5.64 Invention steel
2-5 0.17 0.35 1.28 0.024 0.0023 0.031 0.0024 0.0024 V:0.006 837 0.0057 4.10 Invention steel
2-6 0.19 0.23 1.36 0.015 0.0016 0.028 0.0022 0.0019 Nb:0.028, Ta:0.02 816 0.0044 4.97 Invention steel
2-7 0.15 0.21 1.45 0.017 0.0009 1 0.019 0.0034 0.0028 Nb:0.038 829 0.0043 4.35 Invention steel
2-8 0.15 0.15 1.35 0.018 0.0020 0.037 0.0024 0.0028
Nb:0.056, Ti:0.013,
W:0.035
831 0.0060 3.90 Invention steel
2-9 0.16 0.02 1.12 0.016 0.0021 0.032 0.0022 0.0029 Mo:0.033 829 0.0061 3.12 Invention steel
2-10 0.16 0.06 1.68 0.015 0.0006 '1 0.023 0.0026 0.0025 812 0.0039 5.64 Invention steel
2-11 0.14 0.22 1.48 0.016 0.0023 0.034 0.0028 0.0021
13:0.002, Nb:0.028,
Cu:0.025
831 0.0055 4.23 Invention steel
2-12 0.13 0.14 1.89 0.025 0.0026 0.055 0.0033 0.0022
Nb:0.025, Ti:0.007,
Ni:0.017
826 0.0066 5.82 Invention steel
2-13 0.16 0.04 2.25 0.022 0.0022 0.043 0.0026 0.0026 Cu:0.035, Mg:0.0015 800 0.0062 8.21 Invention steel
2-14 0.14 0.63 1.44 0.017 0.0018 0.027 0.0021 0.0018 Ca:0.0021 846 0.0045 4.05 Invention steel
2-15 0.16 0.21 1.51 0.022 0.0007 0.027 0.0023 0.0015
Nb:0.036, W:0.013,
Y:0.007
827 0.0031 4.88 Invention steel
2-16 0.19 0.15 2.42 0.024 0.0022 0.031 0.0021 0.0019
Nb:0.028, Ti:0.013,
Zr:0.008 788 0.0051 9.74 Invention steel
2-17 0.18 0.18 1.07 0.028 0.0045 1012 0.0019 0.0016 La:0.006 837 0.0065 ' 3.41 Invention steel
[0128]
5
Table 12
Steel Com orients (% by mass) Ae3 A K
No. C Si Mn P S Al N 0 Others (°C) value value
Note
2-18 0.15 0.05 1.87 0.022 0.0038 10.027 0.0023 0.0021
Ni:0.05, Mo:0.021,
Ce:0.008
811 0.0068 6.24 Invention steel
2-19 0.14 0.08 1.15 0.021 0.0033 0.018 0.0038 0.0022
Nb:0.033, Ti:0.018,
Ca:0.0024,
La:0.0028, Ce:0.0063
841 0.0061 2.75 Invention steel
2-20 0.19 0.05 1.56 0.022 0.0045 0.023 0.0032 0.0015
B:0.002, Ni:0.02,
Mo:0.022,
Ca:0.0022,
La:0.0051, Ce:0.012
808 0.0068 5.87 Invention steel
2-21 0.2 0.11 1.46 0.024 0.0026 0.038 0.0026 0.0015
Nb:0.031, Ti:0.008,
Mg:0.0022, Y:0.015,
Zr:0.003, La:0.0035,
Ce:0.0082
813 0.0054 5.67 Invention steel
2-22 0.15 0.18 1.29 0.028 0.0084 0.012 0.0047 0.0029 Y:0.02, Ce:0.012 842 0.0117 3.63
Comparative
example
2-23 0.18
I
0.21 1.64 0.022 0.0090 0.037 0.0023 0.0044 Ni:0.015 815 0.0146 5.97
Comparative
example
2-24 0.15 0.08 1.39 0.021 0.0033 10.125 0.0045 0.0042 Nb:0.033 830 0.0116 4.08
Comparative
example
2-25 0.16 0.05 1.64 0.022 0.0034 0.043 0.0032 0.0029
B:0.002, Mo:0.035,
Ca:0.0027, Y:0.013
819 0.0077 5.46 Invention steel
2-26 0.15 0.11 1.38 0.024 0.0036 0 015 0.0025 0.0045
Nb:0.03I, Ti:0.008,
832 0.0086 4.04
Comparative
Ni:0.02, Ce:0.015 example
2-27 0.18 0.24 2.87 0.026 0.0039 0.047 0.0024 0.0024 Cu:0.024 Mo:0.125 782 0.0079 11.51
, Comparative
example
2-28 0.24 0.10 1.89 0.025 0.0045 0.033 0.0029 0.0025 Nb:0.038, Ni:0.014
784 0.0081 8 63 Comparative
Cu:0 02 .
example
[0129]
Table 13
Hot rolling conditions
Fo ^^ w o o o o T 0 2
0 O CJ
o o°
o
,^ o
M
0 0
-. -.
O C rjl^
'^''^ W LD r^ i-y <9
0
^• M '^ Iuq up N '-^ O N "^ CD ^' O m ^'+. Oa G7 0 `7
O n o
*Z
fv NW O " ^h ,-3 r. O'^
^t O tl4 O ^. .c O O
!-; C7 C
^
., " coo ."-« p CD
ao
-
p, Gq o n CD rn
P N ' o p -:
.
o
°O tD o a p
,
o . i -4 o v
p, '^' m
G ^ as co 0
2-IA 824 1200 1075 77 44.8 1049 20 860 2 15 550 Invention example
2-113 824 1180 1062 52 32.3 1025 22 875 1.5 15 540 Invention example
2-1C 824 1160 1000 66 44.7 962 16 836 5 25 520 Comparative example
2-2A 824 1220 1099 78 37.4 1057 18 870 3 20 500 Invention example
2-2B 824 1100 1072 60 31.2 1026 24 830 1 40 580 Comparative example
2-3A 831 1200 1121 66 44.1 1058 18 860 3 35 550 Invention example
2-3B 831 1150 1041 58 33.3 995 19 841 3 40 530 Comparative example
2-4 820 1150 1091 72 41.8 1031 24 861 6 40 500 Invention example
2-5A 837 1230 1133 55 36.7 1094 25 905 8 50 490 Invention example
2-513 837 1160 1073 57 37.7 1035 24 850 9 30 580 Invention example
2-6A 816 1200 1079 57 32.1 1054 28 869 3 20 450 Invention example
2-6B 816 .1200 1061 59 26.6 1042 16 832 6 25 490 Comparative example
2-7 829 1200 1095 59 31.6 1070 19 880 2 25 480 Invention example
8A 831 1250 1150 63 42.5 1111 19 873 6 15 550 Invention example
2-8B 831 1160 1030 53 36.9 1002 16 806 9 45 570 Comparative example
2-9A 829 1180 1075 63 27.4 1052 18 868 3 20 580 Invention example
2-9B 829 1160 1039 66 32 1012 27 835 0.5 10 530 Comparative exam le
2-9C 829 1150 1052 41 33.2 1028 23 838 3 15 500 "Comparative example
[0130]
Table 14
Hot r lling conditions
c
CD
9
V
D cro
o
re
o° o
rn
va
o
C1
w o
o °
vo o
0 o H
aka ado D
o c
p
°o
o m
o n
o a
ac c
v o
oo
o
aG
rn^a
0
?:
o
o
a o
Ch w
op
p
_
C]
°^° °Q
n
rn
v
o
.
c
M
Z
o
2-10A 812 1160 1063 80 40.7 1032 24 850 6 30 500 Invention example
2-1013 812 1160 1082 53 34.3 1036 11 822 5 10 490 Comparative example
2-11A 831 1200 1096 64 43 1072 22 885 6 40 480 Invention example
2-11B 831 1200 1082 60 42.9 1045 16 870 5 8 520 Comparative example
2-11C 831 1200 1131 55 33.4 1090 27 880 6 50 650 Comparative example
2-12A 826 1250 1125 68 39.6 1103 26 925 9 60 500 Invention example
2-12B 826 1200 1123 58 42.4 1086 18 890 4 45 570 Invention example
2-12C 826 1180 1087 66 41.9 1027 17 840 2 10 630 Comparative example
2-13A 800 1200 1125 76 58.1 1060 34 888 3 35 420 Invention example
2-13B 800 1200 1068 78 59 1026 16 867 5 10 450 Invention example
2-13C 800 1200 1080 73 54.6 992 22 854 6 20 520 Comparative example
2-14 846 1200 1069 72 44.3 1042 24 848 5 15 560 Invention example
2-15 827 1230 1111 64 34.3 1065 28 910 8 60 530 Invention example
2-16 788 1180 1055 68 34.4 1027 27 864 1.5 20 550 Invention example
2-17A 837 1180 1091 66 43 1059 28 856 3 30 500 Invention example
2-17B 837 1180 1050 68 41.2 1026 21 845 3 30 500 Invention example
2-17C 837 1220 1090 60 47.8 1028 19 810 6 15 600 Comparative example
[0131]
Table 15
Hot r0ling conditions
m o o o H ^ m o o a.o
y E5
o CD CD
n
° no 7. a n °
CD ID
° h `i' n CD
-0 °
° ri w a p n ° C] w R n - ao o
h
° ° o
o o m
N
o o r°
^o
o
ric
2-18A 811 1180 1091 59 38.7 1046 21 880 8 40 500 Invention example
2-18B 811 1180 1112 70 35.6 1071 18 872 -6-755 500 Invention example
2-19A 841 1180 1052 60 36.3 1023 23 852 9 40 530 Invention example
2-19B 841 1180 1077 78 56.2 1041 26 849 10 65 550 Invention example
2-20 808 1170 1085 75 44.5 1042 20 889 3 10 480 Invention example
2-21A 813 1250 1161 75 45.2 1123 28 910 8 40 500 Invention example
2-21B 813 1170 1075 60 40.6 1051 18 843 6 10 550 Invention example
2-21C 813 1170 1085 59 36.7 1036 28 835 0.5 15 580 Comparative example
2-22A 842 1200 1079 60 38.7 1025 26 870 3 15 550 Comparative example
2-22B 842 1150 1089 53 37.8 1034 19 867 1.5 15 580 Comparative example
2-23 815 1200 1065 70 38.5 1035 20 858 3 20 580 Comparative example
2-24 830 1150 1053 53 33.6 1028 20 849 6 20 550 Comparative example
2-25 819 1150 1048 54 38.5 1021 18 828 1.5 20 570 Invention example
2-26 832 1180 1080 79 52.7 1042 28 858 1.5 30 540 Comparative example
2-27 782 1150 1066 53 36.8 1034 23 828 1.5 15 580 Comparative example
2-28 784 1150 1060 65 46.1 1026 20 835 2 25 580 Comparative example
74
[0132]
Table 16
Characteristics
of hot-rolled steel plate
Test
specimen
No.
A value K' value
Area fraction of
pearlite bands
having lengths
of 1 mm or
longer (%)
Ultimate
deformability
ratio
(kc/4L)
Note
2-IA 0.0052 3.20 2.7 0.91 invention example
2-1B 0.0052 3.20 2.8 0.92 Invention example
2-1C 0.0052 3.20 4.3 0.74 Comparative example
2-2A 0.0045 3.86 2.1 0.98 Invention example
2-2B 0.0045 3.86 5.2 0.78 Comparative example
2-3A 0.0055 3.84 3.3 0.92 Invention example
2-3B 0.0055 3.84 6.5 0.76 Comparative example
2-4 0.0044 5.64 4.2 0.91 Invention example
2-5A 0.0057 4.10 3.1 0.9 Invention example
2-58 0.0057 4.10 1.9 0.96 Invention example
2-6A 0.0044 4.97 2.5 0.92 Invention example
2-6B 0.0044 4.97 5.51 0.79 Comparative example
2-7 0.0043 4.35 3.2 0.97 Invention example
2-8A 0.006 3.90 2.4 0.91 Invention example
2-8B 0.006 3.90 5.1 0.79 Comparative example
2-9A 0.0061 3.12 2.5 0.96 Invention example
2-9B 0.0061 3.12 4 0.77 Comparative example
2-9C 0.0061 3.12 4.27 0.75 Comparative example
2-I OA 0.0039 5.64 1.5 0.97 Invention example
2-10B 0.0039 5.64 7.3 0.71 Comparative example
2-11A 0.0055 4.23 3.6 0.93 Invention example
2-11B 0.0055 4.23 5.3 0.75 Comparative example
2-11C 0.0055 4.23 6.7 0.72 Comparative example
2-12A 0.0066 5.82 3.8 0.95 Invention example
2-12B 0.0066 5.82 4.9 0.9 Invention example
2-12C 0.0066 5.82 6.8 0.72 Comparative example
[0133]
5
75
Table 17
Characteristics
of hot-rolled steel plate
Test
specimen
No.
A value K value
Area fraction of
pearlite bands
having lengths
of 1 mm or
longer (%
Ultimate
deformability
ratio
Note
2-13A 0.0062 8.21 4.6 0.9 Invention example
2-13B 0.0062 8.21 4.3 0.91 Invention example
2-13C 0.0062 8.21 11.7 0.77 Comparative example
2-14 0.0045 4.05 3.2 0.94 Invention example
2-15 0.0031 4.88 3.5 0.98 Invention example
2-16 0.0054 9.74 6.5 0.9 Invention example
2-17A 0.0065 3.41 2.9 0.91 Invention example
2-17B 0.0065 3.41 3.1 0.92 Invention example
2-17C 0.0065 3.41 4.3 0.77 Comparative example
2-18A 0.0068 6.24 2.5 0.96 Invention example
2-18B 0.0068 6.24 3.8 0.92 Invention example
2-19A 0.0061 2.75 2.6 0.91 Invention example
2-19B 0.0061 2.75 2.5 0.9 Invention example
2-20 0.0068 5.87 4.7 0.92 Invention example
2-21A 0.0054 5.67 3.3 0.94 Invention example
2-21B 0.0054 5.67 4.6 0.92 Invention example
2-21C 0.0054 5.67 6.2 0.71 Comparative example
2-22A 0.0117 3 63_ 3.4 0.65 Comparative example
2-22B 0.0117 3.63 3.6 0.62 Comparative example
2-23 0.0146 5.97 5.2 0.6 Comparative example
2-24 0.0116 4.08 3.9 0.64 Comparative example
2-25 0.0077 5.46 5.1 0.9 Invention example
2-26 0.0086 4.04 3.9 0.73 Comparative example
2-27 0.0079 11.51 12.4 0.72 Comparative example
2-28 0.0081 8.63 9.4 0.75 Comparative example
[0134]
As shown in Tables 2 to 17, the anisotropies in ultimate deformability (ultimate
76
deformation ratios) showed favorable values of 0.9 or more in the steel plates that fulfilled
the component ranges and production conditions of the embodiments. Results were
obtained in which anisotropy in deformability (workability) was small, and the anisotropy
in deformability (workability) is an index of workability effective for preventing
5 occurrence of cracking in a specific direction during plate press forging. In contrast, with
regard to the steel plates of which the components were outside the ranges of the
embodiments, and the steel plates which were manufactured under conditions that did not
fulfill the conditions of the embodiments and which had the components within the ranges
of the embodiments, the ultimate deformability ratios were less than 0.9; and therefore, the
10 anisotropies in deformability (workability) were large.
[0135]
(Example 4)
(Preparation of the surface treatment fluid)
Firstly, surface treatment fluids (chemicals) a to s were prepared which contained
15 the components as shown in the following Tables 18 and 19. Meanwhile, in Tables 18
and 19, in the case where zinc nitrate and phosphate were included as an inorganic
compound andan_acid respectively, zinc phosphate was_presentin the surface treatment
fluid as the inorganic acid salt. It is extremely difficult to dissolve zinc phosphate in
water; however, zinc phosphate dissolves in acid. Therefore, water-soluble zinc nitrate
20 and phosphate were added so as to generate zinc phosphate and make the zinc phosphate
present in the surface treatment fluid.
[0136]
Table 18
Silane coupling agent Inorganic compound Acid Organic compound Lubricant
a Added Added Added Added Added
Type amo t Type amount Type amount Type amount Type amount pH
(g/ ) (g/L) (g/L) (g/L) (g/L)
a 3-aminopropyltrimethoxy silane 12 Zinc nitrate 120 Phosphate 3
Polyamine
120 MoS2 600 4
imide resin
b
N-2-(aminoethyl)-3-
12 Zinc nitrate 30 Phosphate 3 Polyamine
150 MoS2 200 4
aminopropylmethyldimethoxy silane imide resin
c
N-2-(aminoethyl)-3-
12 Zinc nitrate 60 Phosphate 3
Polyamine
150 MoS2 500 4
aminopropylmethyldimethoxy silane imide resin
d
N-2-(aminoethyl)-3-
12 Zinc nitrate 60 Phosphate 3
Polyamine
150 MoS2 2000 4
aminopropylmethyldimethoxy silane imide resin
e N-2-(aminoethyl)-3-
12, Zinc nitrate 60 Phosphate 3
Polyamine
150 MoS2 350 4
aminopropylmethyldimethoxy silane imide resin
f N-2-(aminoethyl)-4-
12
Potassium
60 Phosphate 3
Polyamine
150 PTFE 200 4
amino ro ylmethyldimethoxy silane molybdate imide resin
g
N-2-(aminoethyl)-5- 121 Potassium
60 Phosphate 3
Polyamine
150 ZnO 600 4
aminopropylmethyldimethoxy silane molybdate imide resin
h 3-aminopropyltrimethoxy silane 12 Zinc nitrate 60 Phosphate 3 Polyester
150 MoS2 1100 4
resin
i 3-aminopropyltrimethoxy silane 121 Zinc nitrate 60 Phosphate 3
Epoxy
150 MoS2 5050 4
resin
[0137]
Table 19
Silane coupling agent Inorganic compound Acid Organic compound Lubricant
Added Added Added Added Added pH
Type amount Type amount Type amount Type amount Type amount
(g/L) (gIL) ^g/L) g/L) (g/L)
3-aminopropyltrimethoxy
12 Zinc! nitrate 40 Phosphate 3 Epoxy 4.3 Graphite 25 4
silane resin
k
3-aminopropyltrimethoxy
12
Potassium
1
Polyamine
100 silane silicate MoS2 500 4 imide resin
1
3-aminopropyltrimethoxy
12
Potassium
40 Fluororesin 40 MoS2 4000 4
silane molybdate
m
3-aminopropyltrimethoxy 12 Potassium
40 - - Fluororesin 100 MoS2 170 4 silane tungstate
n
3-aminopropyltrimethoxy
1 Zinc nitrate 120 Phosphate 3
Polyamine
120 Graphite 240 4
silane imide resin
0
3-aminopropyltrimethoxy
100 Zinc nitrate 12 Phosphate 3
Polyamine
12 Graphite 120 4 silane imide resin
P
3-aminopropyltrimethoxy
12 Zinc nitrate 1 Phosphate 0.5
Polyamine
188 MoS2 350 4 silane imide resin
q 3-aminopropyltrimethoxy
12 Zinc nitrate 150 Phosphate 20
Polyamine
17 MoS2 500 4 silane imide resin
r 3-aminopropyltrimethoxy
12 Zinc nitrate 60 Phosphate 3
Polyamine
150 MoS2 100 4 silane imide resin
s 3-aminopropyltrimethoxy
12 Zinc nitrate 5 Phosphate 1
Polyanne
silane imide resin 5 MoS2 1500 4
79
[0138]
(Production of the steel plate for cold forging)
Next, a surface-treated film having a concentration-gradient type three-layer
structure was formed on both surfaces of a hot-rolled steel plate (material, a main body
5 portion of a steel plate) by the following method using any one of the surface treatment
fluids a to s that were prepared in the above-described manner; and thereby, steel plates for
cold forging (Nos. 3-1 to 3-29) were manufactured (refer to the following Table 21).
[0139]
Firstly, a steel having the components as shown in Table 20 were melted through
10 an ordinary converter-vacuum degassing treatment so as to make a slab. Next, hot
rolling, cooling, and coiling were carried out under the conditions of the first embodiment
so as to obtain hot-rolled steel plates (a plate thickness was 0.8 mm).
Any one of the surface treatment fluids a to s was coated on the hot-rolled steel
plate using a coating No. #3 bar so as to form a coated film, and then the coated film was
15 dried. Here, the coating No. #3 bar refers to a bar coater having a coiled wire diameter of
3 mils (1 mil = 25 μm). The drying was carried out under conditions in which an
-achieving temperature-ofthe plate was 150°Cin-"ot air drying furnace having a
temperature of 300°C. After the drying, air-cooling was conducted so as to obtain steel
plates for cold forging.
20 Thicknesses of the respective layers (film thicknesses) were controlled by
adjusting (diluting) concentrations of the surface treatment fluids or adjusting times from
the forming of the coated films to the drying.
[0140]
80
Table 20
Cc Si Mn
P S AAlI N 0
1 .04
0.
U
0.1155 036 ..0044 00.001122 00 000..001166 00..N00003'22 00..00001122
[0141]
(Measurement of film thicknesses (layer thicknesses))
In the present example, the film thicknesses (layer thicknesses) were measured
using a high-frequency GDS. In detail, a depth (a location in the film thickness
direction) of a portion having a peak intensity of half the maximum value of a peak
intensity of a representative element (for example, Mo, C, or the like) of the lubricant
from an outermost surface of the surface-treated film in a measurement chart of the
10 high-frequency GDS was used as a thickness of a lubricant layer. In addition, a depth (a
location in the film thickness direction) of a portion having a peak intensity of half the
maximum value of a peak intensity of a representative element (Si) of the component
originating from the silanol bond from an interface between the surface-treated film and
the hot-rolled steel plate in the measurement chart of the high-frequency GDS was used as
15 a thickness of an adhesion layer. Furthermore, a depth from the portion having a peak
intensity-of halfthe maximum-value of the peakintensity of he representative -clement
(Mo) of the lubricant to the portion having the peak intensity of half the maximum value
of the peal. intensity of the representative element (Si) of the component originating from
the silanol bond was used as a thickness of a base layer. In addition, in the case where
20 the representative elements of the lubricant layer (lubricant component) and the base layer
(inorganic acid salt component) were the same, and in the case where the component
elements of the base layer (inorganic acid salt component) and the adhesion layer
(component originating from the silanol bond) were the same, contents of other elements
were measured so as to obtain the thicknesses.
81
[0142]
However, in the case where graphite was used as the lubricant, the thicknesses of
the lubricant layer and the base layer were measured using the peak intensities of the
representative elements (P, Si, Mo, and W) of the inorganic acid salt.
5 [0143]
(Evaluation method and evaluation standards)
In the present example, film adhesion and workability of the steel plate for cold
forging were evaluated using the evaluation method and the evaluation standards as shown
below.
10 [0144]

The film adhesion was evaluated in a drawing sliding test in which a flat bead
mold was used. An article having a size of 30 mm x 200 mm from which shear burrs at
edges were removed was used as a test specimen. With regard to the test specimen
15 before being slid, fluorescent X-ray intensities of main component elements of the film
were measured using a fluorescent X-ray analyzer.
[01451 -
Surfaces of molds made of SKD 11 which had a length of 40 mm, a width of 60
mm, and a thickness of 30 mm were polished using Emery paper No. #1000 so as to
20 prepare a pair of molds as flat bead molds. Next, the test specimen was sandwiched
between the molds, and the test specimen was drawn using a tension tester in a state where
the molds were pressed down at a pressure of 1000 kg by an air cylinder. With regard to
the test specimen that had undergone the drawing, fluorescent X-ray intensities of the
same elements as described above were measured using the fluorescent X-ray analyzer.
25 Then, a residual rate (intensity after the test/ intensity before the test) x 100 [%] was
82
calculated.
[0146]
Regarding evaluation standards of a film adhesion, a steel plate of which the
residual rate was less than 70% was evaluated as C (Bad), a steel plate which the residual
5 rate was in a range of 70% or more to less than 90% was evaluated as B (Good), and a
steel plate of which the residual rate was 90% or more was evaluated as A (Excellent).
[0147]

Workability was evaluated by a spike test method. In the spike test, a columnar
10 spike test specimen 2 was placed on a die 3 having a funnel-shaped inner surface shape as
shown in FIG. 7A. Next, a load was applied through a plate 1 so as to insert the spike
test specimen 2 into the die 3. Thereby, the spike test specimen 2 was worked into a
shape after the working as shown in FIG 7B. A spike was formed according to the die
shape in the above-described manner, and lubricity was evaluated based on a spike height
15 (mm) at this time. Therefore, a test specimen having a tall spike height is evaluated to be
excellent in the lubricity.
[0148
The workability was evaluated based on the spike height. The spike height of a
sample produced by a chemical reaction/ metal saponification treatment in the related art
20 is in a range of 12.5 mm to 13.5 mm. Therefore, a steel plate of which the spike height
was less than 12.5 mm was evaluated as C (Bad), a steel plate of which the spike height
was in a range of 12.5 mm to 13.5 mm was evaluated as B (Good), and a steel plate of .
which the spike height was more than 13.5 mm was evaluated as A (Excellent).
[0149]
25 The measurement results of the film thicknesses of the respective layers and the
83
evaluation results of the film adhesion and the workability which were obtained in the
above-described manner are shown in Table 21.
Meanwhile, the amount of the inorganic acid salt relative to the amount of the
high-temperature resin in the base layer became the same as the amount of the inorganic
5 acid salt relative to the amount of the high-temperature resin in the surface treatment fluid.
[0150]
84
Table 21
,.a
CD
`.3 W
O
O
N
`C
.F
^
y y
G^ tlQ r
N ' bQ
h¢ O
A
F r
Y
`C ^i',
`C O rn
!y
P.
HO
W
ra
O
N
3-1 a 10 4 100 1 0.25 A A Invention example
3-2 b 15 4 20 0.8 0.2 A A Invention example
3-3 c 10 4 40 1 0.25 A A Invention example
3-4 d 12 0.2 40 0.1 0.5 A B Invention example
3-5 e 13 15 40 7.5 0.5 A B Invention example
3-6 e 13 0.5 40 1 2 A A Invention example
3-7 c 13 3 40 1 0.33 A A Invention example
3-8 c 0.1 4 40 1 0.25 B A Invention example
3-9 c 0.5 4 40 1 0.25 A A Invention example
3-10 c 50 4 40 1 0.25 A A Invention example
3-11 c 100 4 40 1 0.25 B A Invention example
3-12 f 11 4 40 1 0.25 A A Invention example
3-13 g 12 4 40 1 0.25 A A Invention example
3-14 h 11 4 40 10 2.5 A B Invention example
3-15 i 10 4 40 2 0.5 A B Invention example
3-16 j 11 4 1000 1 0.25 A B Invention example
3-17 k 11 4 1 2 0.5 A A Invention example
34-8 12 0.1 X00 1 10 - A Inventionexamples
3-19 m 11 4 40 1 0.25 A A Invention example
3-20 c 13 0.1 40 0.05 0.5 A C Comparative example
3-21 c 12 4 40 12 3 A C Comparative example
3-22 c 12 0.05 40 0.1 2 A C Comparative example
3-23 c 11 16 40 4 0.25 A C Comparative example
3-24 n 0.05 4 100 1 0.25 C C Comparative example
3-25 0 150 2 100 1 0.5 C C Comparative example
3-26 p 14 2 0.8 1 0.5 A C Comparative example
3-27 q 13 2 1200 1 0.5 A C Comparative example
3-28 r 13 10 40 1 0:1 A C Comparative example
3-29 s 12 1 120 15 15 A C Comparative example
85
[0151]
As shown in Table 21, all the invention examples (Nos. 3-1 to 3-19) of the second
embodiment were excellent in the film adhesion and the workability. On the other hand,
the comparative examples (Nos. 3-24 and 3-25) in which the thicknesses of the adhesion
5 layers were outside the range of the second embodiment were poor in the film adhesion
and the workability. Furthermore, the comparative examples (Nos. 3-20 to 3-29) that did
not fulfill any of the requirements as defined in the second embodiment were poor in the
workability (lubricity).
10 INDUSTRIAL APPLICABILITY
[0152]
According to the embodiments of the invention, it is possible to provide a steel
plate for cold forging (hot-rolled steel plate) having anisotropy in ultimate deformability
(ultimate deformation ratio) during cold press forging working of 0.9 or more which
15 indicates that anisotropy in workability is small; and therefore, cracking during press
forging working can be prevented. Furthermore, excellent lubricity and excellent
performance to prevent seizsreand_galling can be achieved by furthedncluding the
surface-treated film according to the embodiment of the invention. Therefore, the
workability in cold molding, so-called plate press forging can be improved. Therefore, in
20 the case where the steel plate for cold forging according to the embodiment of the
invention is used as a material, parts for engines or transmissions which were produced by
hot forging or the like in the related art can be produced by plate press forging. As
described above, the steel plate for cold forging according to the embodiment of the
invention can be widely used as a material for plate press forging.
25
86

CLAIMS
1. A steel plate for cold forging comprising:
a hot-rolled steel plate,
5 wherein the hot-rolled steel plate comprises: in terms of percent by mass,
C: 0.13%to 0.20%;
Si: 0.01% to 0.8%;
Mn: 0.1 % to 2.5%;
P: 0.003% to 0.030%;
10 S: 0.0001 % to 0.008%;
Al: 0.01% to 0.07%;
N: 0.0001% to 0.02%; and
0: 0.0001% to 0.0030%,
with a remainder being Fe and inevitable impurities,
15 an A value represented by the following formula (1) is in a range of 0.0080 or
less,
a thi_cknessofthe hot-rolled steel plate isin arange oft mm to 25 mm, and
an area percentage of pearlite bands having lengths of 1 mm or more is in a range
of not more than a K value represented by the following formula (2) in a region of 4/10t to
20 6/l Ot when a plate thickness is indicated by tin a cross section of a plate thickness that is
parallel to a rolling direction of the hot-rolled steel plate,
A value = 0%+ S%+ 0.033A1% ... (1)
K value = 25.5 x C% + 4.5 x Mn% - 6 • • • (2).
25 2. The steel plate for cold forging according Claim 1,
87
wherein the hot-rolled steel plate further comprises, in terms of percent by mass,
one or more selected from a group consisting of:
Nb: 0.001%to 0.1%;
Ti: 0.001% to 0.05%;
5 V: 0.001%to 0.05%;
Ta: 0.01% to 0.5%; and
W: 0.01% to 0.5%.
3. The steel plate for cold forging according to Claim 1,
10 wherein the hot-rolled steel plate further comprises, in terms of percent by mass,
Cr: 0.01% to 2.0%, and
the area percentage of the pearlite bands having lengths of 1 mm or more is in a
range of not more than a K' value represented by the following formula (3),
K' value ° 15 x C% + 4.5 x Mn% + 3.2 x Cr% - 3.3 • • • (3).
15
4. The steel plate for cold forging according to Claim 1,
wherein-thehot-rolledsteel platefurther compri-ses; in- -terms of percent by mass,
one or more selected from a group consisting of
Ni: 0.01 % to 1.0%;
20 Cu: 0.01% to 1.0%;
Mo: 0.005% to 0.5%; and
B: 0.0005% to 0.01%.
5. The steel plate for cold forging according to Claim 1,
25 wherein the hot-rolled steel plate further comprises, in terms of percent by mass,
88
one or more selected from a group consisting of
Mg: 0.0005% to 0.003%;
Ca: 0.0005% to 0.003%;
Y. 0.001%to 0.03%;
5 Zr: 0.001 % to 0.03%;
La: 0.001% to 0.03%; and
Cc: 0.001%to 0.03%.
6. The steel plate for cold forging according to Claim 1,
10 wherein the steel plate for cold forging further comprises a surface-treated film
provided on either one or both of main surfaces of the hot-rolled steel plate, and the
surface-treated film includes a component originating from a silanol bond represented by
Si-O-X (X represents a metal that is a component of the hot-rolled steel plate), a
high-temperature resin, an inorganic acid salt, and a lubricant,
15 the surface-treated film has a concentration gradient of each component in a film
thickness direction so as to have a concentration-gradient type three-layer structure that
can be identified tape threelayers-ofanadhesion lav r, a base lav, er and a lubricantlayer
situated in series from a side of an interface between the surface-treated film and the
hot-rolled-steel plate,
20 the adhesion layer is a layer that includes a largest amount of the component
originating from the silanol bond among the three layers, and a thickness of the adhesion
layer is in a range of 0.1 nm to 100 nm,
the base layer is a layer that includes largest amounts of the high-temperature
resin and the inorganic acid salt among the three layers, the amount of the inorganic acid
25 salt in the base layer is in a range of I part by mass to 100 parts by mass with respect to
89
100 parts by mass of the high-temperature resin, and a thickness of the base layer is in a
range of 0.1 pm to 15 Vim,
the lubricant layer is a layer that includes a largest amount of the lubricant among
the three layers, and a thickness of the lubricant layer is in a range of 0.1 μm to 10 μm,
and
a ratio of the thickness of the lubricant layer to the thickness of the base layer is
in a range of 0.2 to 10.
7. The steel plate for cold forging according to Claim 6,
10 wherein the inorganic acid salt is at least one compound selected from a group
consisting of phosphate, borate, silicate, molybdate, and tungstate.
8. The steel plate for cold forging according to Claim 6,
wherein the high-temperature resin is a polyimide resin.
15
9. The steel plate for cold forging according to Claim 6,
wherein the lubricant is-at-least-ene-seleeted-from a group-consisting of
polytetralluoroethylene, molybdenum disulfide, tungsten disulfide, zinc oxide, and
graphite.
20
10. A method for producing a steel plate for cold forging, the method comprising:
heating a slab at a temperature of 1150°C to 1300°C;
subjecting the heated slab to rough rolling at a temperature of 1020°C or higher
so as to make a rough bar;
90
subjecting the rough bar to finishing rolling under a condition where a finishing
temperature is in a range of Ae3 or higher so as to make a rolled material;
after the finishing rolling, subjecting the rolled material to air cooling for 1
second to 10 seconds;
5 after the air cooling, cooling the rolled material at a cooling rate of 10°C/s to
70°C/s to a coiling temperature; and
coiling the cooled rolled material at the coiling temperature of 400°C to 580°C so
as to make a hot-rolled steel plate,
wherein the slab comprise: in terms of percent by mass, C: 0.13% to 0.20%; Si:
10 0.01% to 0.8%; Mn: 0.1% to 2.5%; P: 0.003% to 0.030%; S: 0.0001% to 0.006%, Al:
0.01% to 0.07%, N: 0.0001% to 0.02%, and 0: 0.0001% to 0.0030% with a remainder
being Fe and inevitable impurities, and an A value represented by the following formula
(1) is in a range of 0.0080 or less,
the rough rolling comprises a first rolling and a second rolling that is carried out
15 30 seconds or more after an end of the first rolling,
the first rolling is carried out under conditions where a temperature is in a range
of 1020°C or higher and a sum of rolling reduction rates is in a range ot5O% or more, and
the second rolling is carried out under conditions where a temperature is in a
range of 1020°C or higher and a sum of rolling reduction rates is in a range of 15% to
20 30%,
A value = 0% + S% + 0.033A1% ... (1).
11. The method for producing a steel plate for cold forging according to Claim 10,
wherein the method further comprises:
91
coating a water-based surface treatment fluid including a water-soluble silane
coupling agent, a water-soluble inorganic acid salt, a water-soluble high-temperature resin,
and a lubricant on either one or both of main surfaces of the hot-rolled steel plate so as to
form a coated film; and
5 drying the coated films so as to form a surface-treated film on either one or both
of the main surfaces of the hot-rolled steel plate.

Documents

Application Documents

# Name Date
1 6474-DELNP-2012-IntimationOfGrant07-04-2021.pdf 2021-04-07
1 Power of Authority.pdf 2012-07-23
2 6474-DELNP-2012-PatentCertificate07-04-2021.pdf 2021-04-07
2 Form-5.doc 2012-07-23
3 Form-3.doc 2012-07-23
3 6474-DELNP-2012-Correspondence-090719.pdf 2019-07-13
4 Form-1.pdf 2012-07-23
4 6474-DELNP-2012-OTHERS-090719.pdf 2019-07-13
5 Drawings.pdf 2012-07-23
5 6474-DELNP-2012-Power of Attorney-090719.pdf 2019-07-13
6 6474-delnp-2012-Form-18-(25-07-2012).pdf 2012-07-25
6 6474-DELNP-2012-FORM 13 [08-07-2019(online)].pdf 2019-07-08
7 6474-DELNP-2012-RELEVANT DOCUMENTS [08-07-2019(online)].pdf 2019-07-08
7 6474-delnp-2012-Correspondence Others-(25-07-2012).pdf 2012-07-25
8 6474-DELNP-2012-ABSTRACT [08-05-2018(online)].pdf 2018-05-08
8 6474-DELNP-2012-Correspondence-others-(18-09-2012).pdf 2012-09-18
9 6474-DELNP-2012-CLAIMS [08-05-2018(online)].pdf 2018-05-08
10 6474-DELNP-2012-FER_SER_REPLY [08-05-2018(online)].pdf 2018-05-08
10 6474-delnp-2012-Form-3-(14-12-2012).pdf 2012-12-14
11 6474-DELNP-2012-Correspondence-040418.pdf 2018-04-12
11 6474-delnp-2012-GPA-(28-06-2013).pdf 2013-06-28
12 6474-delnp-2012-Form-2-(28-06-2013).pdf 2013-06-28
12 6474-DELNP-2012-OTHERS-040418.pdf 2018-04-12
13 6474-delnp-2012-Form-1-(28-06-2013).pdf 2013-06-28
13 6474-DELNP-2012-Power of Attorney-040418.pdf 2018-04-12
14 6474-DELNP-2012-COMPLETE SPECIFICATION [03-04-2018(online)].pdf 2018-04-03
14 6474-delnp-2012-Correspondence-Others-(28-06-2013).pdf 2013-06-28
15 6474-DELNP-2012-CORRESPONDENCE [03-04-2018(online)].pdf 2018-04-03
15 6474-DELNP-2012-FER.pdf 2018-01-04
16 6474-DELNP-2012-DRAWING [03-04-2018(online)].pdf 2018-04-03
16 6474-DELNP-2012-Proof of Right (MANDATORY) [03-04-2018(online)].pdf 2018-04-03
17 6474-DELNP-2012-PETITION UNDER RULE 137 [03-04-2018(online)].pdf 2018-04-03
17 6474-DELNP-2012-FER_SER_REPLY [03-04-2018(online)].pdf 2018-04-03
18 6474-DELNP-2012-FORM 3 [03-04-2018(online)].pdf 2018-04-03
18 6474-DELNP-2012-OTHERS [03-04-2018(online)].pdf 2018-04-03
19 6474-DELNP-2012-FORM-26 [03-04-2018(online)].pdf 2018-04-03
19 6474-DELNP-2012-Information under section 8(2) (MANDATORY) [03-04-2018(online)].pdf 2018-04-03
20 6474-DELNP-2012-FORM-26 [03-04-2018(online)].pdf 2018-04-03
20 6474-DELNP-2012-Information under section 8(2) (MANDATORY) [03-04-2018(online)].pdf 2018-04-03
21 6474-DELNP-2012-FORM 3 [03-04-2018(online)].pdf 2018-04-03
21 6474-DELNP-2012-OTHERS [03-04-2018(online)].pdf 2018-04-03
22 6474-DELNP-2012-FER_SER_REPLY [03-04-2018(online)].pdf 2018-04-03
22 6474-DELNP-2012-PETITION UNDER RULE 137 [03-04-2018(online)].pdf 2018-04-03
23 6474-DELNP-2012-DRAWING [03-04-2018(online)].pdf 2018-04-03
23 6474-DELNP-2012-Proof of Right (MANDATORY) [03-04-2018(online)].pdf 2018-04-03
24 6474-DELNP-2012-CORRESPONDENCE [03-04-2018(online)].pdf 2018-04-03
24 6474-DELNP-2012-FER.pdf 2018-01-04
25 6474-DELNP-2012-COMPLETE SPECIFICATION [03-04-2018(online)].pdf 2018-04-03
25 6474-delnp-2012-Correspondence-Others-(28-06-2013).pdf 2013-06-28
26 6474-delnp-2012-Form-1-(28-06-2013).pdf 2013-06-28
26 6474-DELNP-2012-Power of Attorney-040418.pdf 2018-04-12
27 6474-delnp-2012-Form-2-(28-06-2013).pdf 2013-06-28
27 6474-DELNP-2012-OTHERS-040418.pdf 2018-04-12
28 6474-delnp-2012-GPA-(28-06-2013).pdf 2013-06-28
28 6474-DELNP-2012-Correspondence-040418.pdf 2018-04-12
29 6474-delnp-2012-Form-3-(14-12-2012).pdf 2012-12-14
29 6474-DELNP-2012-FER_SER_REPLY [08-05-2018(online)].pdf 2018-05-08
30 6474-DELNP-2012-CLAIMS [08-05-2018(online)].pdf 2018-05-08
31 6474-DELNP-2012-ABSTRACT [08-05-2018(online)].pdf 2018-05-08
31 6474-DELNP-2012-Correspondence-others-(18-09-2012).pdf 2012-09-18
32 6474-delnp-2012-Correspondence Others-(25-07-2012).pdf 2012-07-25
32 6474-DELNP-2012-RELEVANT DOCUMENTS [08-07-2019(online)].pdf 2019-07-08
33 6474-DELNP-2012-FORM 13 [08-07-2019(online)].pdf 2019-07-08
33 6474-delnp-2012-Form-18-(25-07-2012).pdf 2012-07-25
34 6474-DELNP-2012-Power of Attorney-090719.pdf 2019-07-13
34 Drawings.pdf 2012-07-23
35 Form-1.pdf 2012-07-23
35 6474-DELNP-2012-OTHERS-090719.pdf 2019-07-13
36 6474-DELNP-2012-Correspondence-090719.pdf 2019-07-13
37 6474-DELNP-2012-PatentCertificate07-04-2021.pdf 2021-04-07
38 Power of Authority.pdf 2012-07-23
38 6474-DELNP-2012-IntimationOfGrant07-04-2021.pdf 2021-04-07

Search Strategy

1 keywords_11-12-2017.pdf

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