[0001]
The present invention relates to a method for producing a grain oriented
electrical steel sheet.
Priority is claimed on Japanese Patent Application No. 2019-004868, filed on
January 16, 2019, and the content of which is incorporated herein by reference.
Background Art
[0002]
A grain oriented electrical steel sheet is used mainly in a transformer. A
transformer is continuously excited over a long period of time from installation to disuse
15 such that energy loss continuously occurs. Therefore, energy loss occurring when the
transformer is magnetized by an alternating current, that is, iron loss is a main index that
determines the performance of the transformer.
[0003]
In order to reduce iron loss of a grain-oriented electrical steel sheet, various
20 methods have been developed. Examples of the methods include a method of highly
aligning grains in the { 110} <00 1 > orientation called Goss orientation in a crystal
structure, a method of increasing the content of a solid solution element such as Si that
increases electric resistance in a steel sheet, and a method of reducing the thickness of a
steel sheet.
25 [0004]
2
In addition, it is known that a method of applying tension to a steel sheet is
effective for reducing iron loss. Thus, in general, in order to reduce the iron loss, an
insulation coating is formed on a surface of the grain oriented electrical steel sheet. The
coating applies the tension to the grain oriented electrical steel sheet, and thereby,
5 reduces the iron loss as a single steel sheet. Moreover, the coating ensures interlaminar
electrical insulation when the grain oriented electrical steel sheets are utilized after being
laminated, and thereby, reduces the iron loss as an iron core.
[0005]
For instance, as the grain oriented electrical steel sheet with the coating, a
10 forsterite film which is an oxide film including Mg is formed on a surface of a base steel
sheet, and then, the insulation coating is formed on a surface of the forsterite film. In
the case, the coating on the base steel sheet includes the forsterite film and the insulation
coating. The forsterite film and the insulation coating respectively have a function of
increasing the electrical insulation and applying the tension to the base steel sheet.
15 [0006]
The forsterite film which is the oxide film including Mg is formed, during final
annealing which is a heat treatment at 900 to 1200°C for 30 hours or more to make the
steel sheet be secondary-recrystallized, by reacting an annealing separator mainly
including magnesia (MgO) with silicon dioxide (Si02) formed on the base steel sheet
20 during decarburization annealing.
[0007]
The insulation coating is formed by applying coating solution including, for
instance, phosphoric acid or phosphate, colloidal silica, and chromic anhydride or
chromate to the base steel sheet after final annealing, and by baking and drying it at 300
25 to 950°C for 10 seconds or more.
5
3
[0008]
In order that the coating ensures the function of increasing the insulation and
applying the tension to the base steel sheet, sufficient adhesion is required between the
coating and the base steel sheet.
[0009]
Conventionally, the above adhesion has been mainly ensured by the anchor
effect derived from the unevenness of an interface between the base steel sheet and the
forsterite film. However, in recent years, it has been found that the unevenness of the
interface becomes an obstacle of movement of a magnetic domain wall when the grain
10 oriented electrical steel sheet is magnetized, and thus, the unevenness is also a factor that
hinders the reduction of iron loss.
[0010]
For instance, Japanese Unexamined Patent Application, First Publication No.
S49-096920 (Patent Document 1) and PCT International Publication No.
15 W02002/088403 (Patent Document 2) disclose a technique to ensure the adhesion of the
insulation coating even in a state in which the forsterite film which is the oxide film
including Mg does not exist and the interface is smooth in order to further reduce the iron
loss.
20
[0011]
In the method for producing the grain oriented electrical steel sheet as disclosed
in the Patent Document 1, the forsterite film is removed by pickling or the like and then
the surface of the base steel sheet is smoothened by chemical polishing or electrolytic
polishing. In the method for producing the grain oriented electrical steel sheet as
disclosed in the Patent Document 2, the formation of the forsterite film itself is
25 suppressed by using an annealing separator containing alumina (Ah03) for the final
4
annealing and thereby the surface of the base steel sheet is smoothened.
[0012]
However, in the producing methods as disclosed in the Patent Document 1 and
the Patent Document 2, there is a problem that the insulation coating is difficult to adhere
5 to the surface of the base steel sheet (sufficient adhesion is not obtained) in a case where
the insulation coating is formed in contact with the surface of the base steel sheet
(directly on the surface of the base steel sheet).
Related Art Documents
10 Patent Documents
15
[0013]
[Patent Document 1] Japanese Unexamined Patent Application, First
Publication No. S49-096920
[Patent Document 2] PCT International Publication No. W02002/088403
Summary of Invention
Technical Problem to be Solved
[0014]
The present invention has been made in consideration of the above mentioned
20 situations. An object of the invention is to provide a method for producing a grain
oriented electrical steel sheet without the forsterite film and excellent in magnetic
characteristics (in particular, iron loss) and the coating adhesion.
Solution to Problem
25 [0015]
5
The present inventors have investigated a technique to improve the adhesion
(coating adhesion) between the steel sheet and the insulation coating even in a case
where the forsterite film is not formed for reducing the iron loss and the insulation
coating is formed on the surface of the grain oriented electrical steel sheet in which the
5 surface of the steel sheet is smoothened.
[0016]
As a result, it has been found that it is possible to produce the grain oriented
electrical steel sheet without the forsterite film and excellent in the magnetic
characteristics and the coating adhesion by appropriate! y combining predetermined
10 processes.
15
20
25
[0017]
An aspect of the present invention employs the following.
( 1) A method for producing a grain oriented electrical steel sheet according to
an aspect of the present invention includes:
a hot rolling process of hot-rolling a steel piece to obtain a hot rolled steel sheet,
the steel piece including, as a chemical composition, by mass%,
0.030 to 0.100% of C,
0.80 to 7.00% of Si,
0.01 to 1.00% of Mn,
0 to 0.060% in total of S and Se,
0.010 to 0.065% of acid soluble Al,
0.004 to 0.012% ofN,
0 to 0.30% of Cr,
0 to 0.40% of Cu,
0 to 0.50% of P,
5
10
15
0 to 0.30% of Sn,
0 to 0.30% of Sb,
0 to 1.00% ofNi,
0 to 0.008% ofB,
0 to 0.15% ofV,
0 to 0.20% of Nb,
0 to 0.10% ofMo,
0 to 0.015% of Ti,
0 to 0.010% ofBi, and
6
a balance consisting of Fe and impurities;
a cold rolling process of cold-rolling the hot rolled steel sheet to obtain a cold
rolled steel sheet;
a decarburization annealing process of decarburization -annealing the cold rolled
steel sheet to obtain a decarburization annealed sheet;
an annealing separator applying process of applying and drying an annealing
separator including MgO to the decarburization annealed sheet;
a final annealing process of final-annealing the decarburization annealed sheet
after applying the annealing separator to obtain a final annealed sheet;
an annealing separator removing process of removing a redundant annealing
20 separator from a surface of the final annealed sheet; and
an insulation coating forming process of forming an insulation coating on the
surface of the final annealed sheet,
wherein, in the decarburization annealing process,
PH20/PH2 which is an oxidation degree of an atmosphere is 0.18 to 0.80, an
25 annealing temperature is 750 to 900°C, and a holding is 10 to 600 seconds,
5
10
15
20
7
wherein, in the annealing separator applying process,
the annealing separator further includes MCl which is at least one selected from
chlorides of an alkali metal, an alkaline earth metal, and Bi, and MCl I MgO which is a
mass ratio of MgO and MCl is 2 to 40%,
wherein, in the final annealing process,
an oxidation degree is 0.00010 to 0.2 when an atmosphere includes a hydrogen,
or a dew point is 0°C or less when an atmosphere consists of an inert gas without a
hydrogen, and
wherein, in the insulation coating forming process,
the insulation coating is formed by applying an insulation coating forming
solution which mainly includes a phosphate or a colloidal silica, by baking at 350 to
600°C, and then by heat-treating at 800 to 1000°C.
(2) The method for producing the grain oriented electrical steel sheet
according to (1) may include,
between the hot rolling process and the cold rolling process,
at least one of a hot band annealing process of annealing the hot rolled steel
sheet or a hot band pickling process of pickling the hot rolled steel sheet.
(3) In the method for producing the grain oriented electrical steel sheet
according to (1) or (2),
in the decarburization annealing process, a nitriding treatment may be conducted
by annealing the cold rolled steel sheet in an atmosphere including ammonia.
( 4) The method for producing the grain oriented electrical steel sheet
according to any one of (1) to (3) may include,
between the cold rolling process and the decarburization annealing process,
25 between the decarburization annealing process and the annealing separator applying
5
8
process, between the annealing separator removing process and the insulation coating
forming process, or after the insulation coating forming process,
a magnetic domain refining process of conducting a magnetic domain refining
treatment.
( 5) In the method for producing the grain oriented electrical steel sheet
according to any one of (1) to (4),
in the annealing separator removing process, a pickling may be conducted after
water-washing using an acidic solution whose volume concentration is less than 20%.
( 6) In the method for producing the grain oriented electrical steel sheet
10 according to any one of (1) to (5),
15
20
25
the steel piece may include, as the chemical composition, by mass%, at least one
selected from a group consisting of
0.02 to 0.30% of Cr,
0.05 to 0.40% of Cu,
0.005 to 0.50% of P,
0.02 to 0.30% of Sn,
0.01 to 0.30% of Sb,
0.01 to 1.00% of Ni,
0.0005 to 0.008% of B,
0.002 to 0.15% ofV,
0.005 to 0.20% of Nb,
0.005 to 0.10% ofMo,
0.002 to 0.015% ofTi, and
0.001 to 0.010% ofBi.
9
Effects of Invention
[0018]
According to the above aspects of the present invention, it is possible to provide
the method for producing the grain oriented electrical steel sheet without the forsterite
5 film and excellent in the magnetic characteristics and the coating adhesion.
Brief Description of Drawings
[0019]
Fig. 1 is a flow chart illustrating a method for producing a grain oriented
10 electrical steel sheet according to an embodiment of the present invention.
Detailed Description of Preferred Embodiments
[0020]
Hereinafter, a preferable embodiment of the present invention is described in
15 detail. However, the present invention is not limited only to the configuration which is
disclosed in the embodiment, and various modifications are possible without departing
from the aspect of the present invention. In addition, the limitation range as described
in the embodiment includes a lower limit and an upper limit thereof. However, the
value expressed by "more than" or "less than" does not include in the limitation range.
20 "%"of the amount of respective elements expresses "mass%".
[0021]
A method for producing a grain oriented electrical steel sheet according to an
embodiment of the present invention (hereinafter, referred to as "the method for
producing the grain oriented electrical steel sheet according to the embodiment") is the
25 method for producing the grain oriented electrical steel sheet without a forsterite film and
10
includes the following processes.
( i) Hot rolling process of hot-rolling a steel piece including predetermined
chemical composition to obtain a hot rolled steel sheet.
( ii) Cold rolling process of cold-rolling the hot rolled steel sheet by cold-rolling
5 once or by cold-rolling plural times with an intermediate annealing to obtain a cold rolled
steel sheet.
(iii) Decarburization annealing process of decarburization-annealing the cold
rolled steel sheet to obtain a decarburization annealed sheet.
( iv ) Annealing separator applying process of applying and drying an annealing
10 separator including MgO to the decarburization annealed sheet.
( v ) Final annealing process of final-annealing the decarburization annealed
sheet after applying the annealing separator to obtain a final annealed sheet.
( vi ) Annealing separator removing process of removing a redundant annealing
separator from a surface of the final annealed sheet by methods including one or both of
15 water-washing and pickling.
( vii ) Insulation coating forming process of forming an insulation coating on the
surface of the final annealed sheet.
[0022]
In addition, the method for producing the grain oriented electrical steel sheet
20 according to the embodiment may further include the following processes.
25
( I ) Hot band annealing process of annealing the hot rolled steel sheet.
( II ) Hot band pickling process of pickling the hot rolled steel sheet.
( III ) Magnetic domain refining process of conducting a magnetic domain
refining treatment.
[0023]
11
In the method for producing the grain oriented electrical steel sheet according to
the embodiment, it is necessary to control not only one process in the above processes
but each of the above processes comprehensively and inseparably. Only when the
predetermined conditions in each of all processes as explained above are controlled, it is
5 possible to reduce the iron loss and improve the coating adhesion.
10
15
20
25
[0024]
Hereinafter, each process is described in detail.
[0025]
< Hot rolling process >
In the hot rolling process, the steel piece is hot-rolled to obtain the hot rolled
steel sheet, the steel piece including, as the chemical composition, by mass%,
0.030 to 0.100% of C,
0.80 to 7.00% of Si,
0.01 to 1.00% of Mn,
0 to 0.060% in total of S and Se,
0.010 to 0.065% of acid soluble Al,
0.004 to 0.012% ofN,
0 to 0.30% of Cr,
0 to 0.40% of Cu,
0 to 0.50% of P,
0 to 0.30% of Sn,
0 to 0.30% of Sb,
0 to 1.00% ofNi,
0 to 0.008% ofB,
0 to 0.15% ofV,
5
0 to 0.20% of Nb,
0 to 0.10% ofMo,
0 to 0.015% of Ti,
0 to 0.010% ofBi, and
12
a balance consisting of Fe and impurities. In the embodiment, the steel sheet
after the hot rolling process is referred to as the hot rolled steel sheet.
[0026]
The method for making the steel piece (slab) to be used in the hot rolling
process is not limited. For instance, molten steel with predetermined chemical
10 composition may be made, and the slab may be made by using the molten steel. The
slab may be made by continuous casting. An ingot may be made by using the molten
steel, and then, the slab may be made by blooming the ingot. Moreover, the slab may
be made by other methods.
15
20
[0027]
A thickness of the slab is not particular! y limited. The thickness of the slab
may be 150 to 350 mm for instance. The thickness of the slab is preferably 220 to 280
mm. The slab with the thickness of 10 to 70 mm which is a so-called thin slab may be
used.
[0028]
Limitation reasons of the chemical composition of the steel piece are explained.
Hereinafter,"%" of the chemical composition represents "mass%".
[0029]
( 0.030 to 0.100% ofC)
C (carbon) is an element effective in controlling the primary recrystallized
25 structure, but negatively affective in the magnetic characteristics. Thus, Cis the
5
13
element to be removed by decarburization annealing before final annealing. When the
C content is more than 0.100%, a time for decarburization annealing needs to be
prolonged, and the productivity decreases. Thus, the C content is to be 0.100% or less.
The C content is preferably 0.085% or less, and more preferably 0.070% or less.
[0030]
It is favorable that the C content is lower. However, when considering the
productivity in industrial production and the magnetic characteristics of the product, the
lower limit of the C content is substantially 0.030%.
[0031]
10 ( 0.80 to 7.00% of Si)
Si (silicon) increases the electric resistance of grain oriented electrical steel sheet,
and thereby, reduces the iron loss. When the Si content is less than 0.80%, y
transformation occurs during the final annealing and the crystal orientation of grain
oriented electrical steel sheet is impaired. Thus, the Si content is to be 0.80% or more.
15 The Si content is preferably 2.00% or more, and more preferably 2.50% or more.
20
On the other hand, when the Si content is more than 7.00%, the cold workability
deteriorates and the cracks tend to occur during cold rolling. Thus, the Si content is to
be 7.00% or less. The Si content is preferably 4.50% or less, and more preferably
4.00% or less.
[0032]
( 0.01 to 1.00% of Mn)
Mn (manganese) increases the electric resistance of grain oriented electrical
steel sheet, and thereby, reduces the iron loss. Moreover, Mn forms MnS and/or MnSe
which act as the inhibitor by bonding to Sand/or Se. When the Mn content is within
25 0.01 to 1.00%, the secondary recrystallization becomes stable. Thus, the Mn content is
14
to be 0.01 to 1.00%. The lower limit of the Mn content is preferably 0.08%, and more
preferably 0.09%. The upper limit of the Mn content is preferably 0.50%, and more
preferably 0.20%.
[0033]
5 ( 0 to 0.060% in total of one or both of Sand Se)
S (sulfur) and Se (selenium) are elements to form MnS and/or MnSe which act
as the inhibitor by bonding to Mn.
When the total amount of one or both of Sand Se (S + Se) is more than 0.060%,
the dispersion state of precipitation of MnS and/or MnSe becomes uneven. In the case,
10 the desired secondary recrystallized structure cannot be obtained, and the magnetic flux
density may decrease. Moreover, MnS remains in the steel after purification annealing,
and the hysteresis loss may increase. Thus, the total amount of S and Se is to be
0.060% or less.
The lower limit of the total amount of S and Se is not particular! y limited, and
15 may be 0%. The lower limit thereof may be 0.003%. When the inhibitor thereof is
used, the lower limit is preferably 0.015%.
[0034]
( 0.010 to 0.065% of acid soluble Al (Sol. Al))
The acid soluble Al (aluminum) is an element to form (Al, Si)N which acts as
20 the inhibitor by bonding toN. When the amount of acid soluble Al is less than 0.010%,
the effect of addition is not sufficiently obtained, and the secondary recrystallization does
not proceed sufficiently. Thus, the amount of acid soluble Al is to be 0.010% or more.
The amount of acid soluble Al is preferably 0.015% or more, and more preferably
0.020% or more.
25 [0035]
15
On the other hand, when the amount of acid soluble Al is more than 0.065%, the
dispersion state of precipitation of AlN and/or (Al, Si)N becomes uneven, the desired
secondary recrystallized structure cannot be obtained, and the magnetic flux density
decreases. Thus, the amount of acid soluble Al (Sol. Al) is to be 0.065% or less. The
5 amount of acid soluble Al is preferably 0.055% or less, and more preferably 0.050% or
less.
[0036]
( 0.004 to 0.012% of N)
N (nitrogen) is an element to form AlN and/or (Al, Si)N which act as the
10 inhibitor by bonding to Al. When theN content is less than 0.004%, the formation of
AlN and/or (Al, Si)N becomes insufficient. Thus, theN content is to be 0.004% or
more. TheN content is preferably 0.006% or more, and more preferably 0.007% or
more.
On the other hand, when theN content is more than 0.012%, the blisters (voids)
15 may be formed in the steel sheet. Thus, theN content is to be 0.012% or less.
[0037]
The steel piece includes, as the chemical composition, the above elements, and
the balance consists of Fe and impurities. However, in consideration of the influence on
the magnetic characteristics and the improvement of the inhibitors functions by forming
20 compounds, the steel piece may include at least one of optional elements as substitution
for a part of Fe. For instance, the optional elements included as substitution for a part
of Fe may be Cr, Cu, P, Sn, Sb, Ni, B, V, Nb, Mo, Ti, and Bi. However, the optional
elements do not need to be included, the lower limits thereof may be 0% respectively.
Moreover, even if the optional elements may be included as impurities, the above
25 mentioned effects are not affected. Herein, the impurities correspond to elements which
5
16
are contaminated during industrial production of steel from ores and scrap that are used
as a raw material of steel, or from environment of a production process.
[0038]
( 0 to 0.30% ofCr)
Cr (chrome) is an element effective in increasing the electric resistance, and
thereby, reducing the iron loss, in common with Si. Thus, Cr may be included. In
order to obtain the above effects, the Cr content is preferably 0.02% or more, and more
preferably 0.05% or more.
On the other hand, when the Cr content is more than 0.30%, the magnetic flux
10 density may deteriorate. Thus, the upper limit of the Cr content is preferably 0.30%,
more preferably 0.20%, and further more preferably 0.12%.
[0039]
( 0 to 0.40% of Cu )
Cu (copper) is also an element effective in increasing the electric resistance, and
15 thereby, reducing the iron loss. Thus, Cu may be included. In order to obtain the
above effects, the Cu content is preferably 0.05% or more, and more preferably 0.10% or
more.
On the other hand, when the Cu content is more than 0.40%, the improvement
effect of reducing the iron loss may be saturated, and surface defects called "copper scab"
20 may be incurred during hot rolling. Thus, the upper limit of the Cu content is preferably
0.40%, more preferably 0.30%, and further more preferably 0.20%.
[0040]
( 0 to 0.50% ofP)
P (phosphorus) is also an element effective in increasing the electric resistance,
25 and thereby, reducing the iron loss. Thus, P may be included. In order to obtain the
17
above effects, the P content is preferably 0.005% or more, and more preferably 0.010%
or more.
On the other hand, when the P content is more than 0.50%, the rollability may
deteriorate. Thus, the upper limit of the P content is preferably 0.50%, more preferably
5 0.20%, and further more preferably 0.15%.
[0041]
( 0 to 0.30% of Sn )
( 0 to 0.30% of Sb )
Sn (tin) and Sb (antimony) are elements effective in stabilizing the secondary
10 recrystallization, and thereby, developing the { 110}<001> orientation. Thus, Sn and Sb
may be included. In order to obtain the above effects, the Sn content is preferably
0.02% or more, and more preferably 0.05% or more. Moreover, the Sb content is
preferably 0.01% or more, and more preferably 0.03% or more.
On the other hand, when the Sn content is more than 0.30% or when the Sb
15 content is more than 0.30%, the magnetic characteristics may deteriorate. Thus, the
upper limits of the Sn content and the Sb content are preferably 0.30% respectively.
The upper limit of the Sn content is preferably 0.15%, and more preferably 0.10%.
Moreover, the upper limit of the Sb content is preferably 0.15%, and more preferably
0.10%.
20 [0042]
( 0 to 1.00% ofNi)
Ni (nickel) is also an element effective in increasing the electric resistance, and
thereby, reducing the iron loss. Moreover, Ni is an element effective in controlling the
metallographic structure of the hot rolled steel sheet, and thereby, improving the
25 magnetic characteristics. Thus, Ni may be included. In order to obtain the above
5
10
18
effects, the Ni content is preferably 0.01% or more, and more preferably 0.02% or more.
On the other hand, when the Ni content is more than 1.00%, the secondary
recrystallization may be unstable. Thus, the Ni content is preferably 1.00% or less,
more preferably 0.20% or less, and further more preferably 0.10% or less.
[0043]
( 0 to 0.008% ofB)
B (boron) is an element effective in forming BN which acts as the inhibitor by
bonding toN. Thus, B may be included. In order to obtain the above effects, the B
content is preferably 0.0005% or more, and more preferably 0.0010% or more.
On the other hand, when the B content is more than 0.008%, the magnetic
characteristics may deteriorate. Thus, the upper limit of the B content is preferably
0.008%, more preferably 0.005%, and further more preferably 0.003%.
[0044]
( 0 to 0.15% ofV)
15 ( 0 to 0.20% ofNb)
( 0 to 0.015% of Ti)
V (vanadium), Nb (niobium), and Ti (titanium) are elements which act as the
inhibitor by bonding to N, C, and the like. Thus, V, Nb, and Ti may be included. In
order to obtain the above effects, the V content is preferably 0.002% or more, and more
20 preferably 0.010% or more. The Nb content is preferably 0.005% or more, and more
preferably 0.020% or more. The Ti content is preferably 0.002% or more, and more
preferably 0.004% or more.
On the other hand, when the V content is more than 0.15%, when the Nb content
is more than 0.20%, or when the Ti content is more than 0.015% in the steel piece, there
25 elements may remain in the final product. In the case, as the final product, the V
19
content may be more than 0.15%, the Nb content may be more than 0.20%, or the Ti
content may be more than 0.015%. As a result, the magnetic characteristics of the final
product (grain oriented electrical steel sheet) may deteriorate.
Thus, the upper limit of the V content is preferably 0.15%, more preferably
5 0.10%, and further more preferably 0.05%. The upper limit of the Ti content is
preferably 0.015%, more preferably 0.010%, and further more preferably 0.008%. Thus,
the upper limit of the Nb content is preferably 0.20%, more preferably 0.10%, and further
more preferably 0.08%.
[0045]
10 ( 0 to 0.10% ofMo)
15
20
Mo (molybdenum) is also an element effective in increasing the electric
resistance, and thereby, reducing the iron loss. Thus, Mo may be included. In order to
obtain the above effects, the Mo content is preferably 0.005% or more, and more
preferably 0.01% or more.
On the other hand, when the Mo content is more than 0.1 0%, the rollability of
the steel sheet may deteriorate. Thus, the upper limit of the Mo content is preferably
0.10%, more preferably 0.08%, and further more preferably 0.05%.
[0046]
( 0 to 0.010% ofBi)
Bi (bismuth) is an element effective in stabilizing precipitates such as sulfide,
and thereby, improving the inhibitors functions. Thus, Bi may be included. In order to
obtain the above effects, the Bi content is preferably 0.001% or more, and more
preferably 0.002% or more.
On the other hand, when the Bi content is more than 0.010%, the magnetic
25 characteristics may deteriorate. Thus, the upper limit of the Bi content is preferably
20
0.010%, more preferably 0.008%, and further more preferably 0.006%.
[0047]
The chemical composition as described above may be measured by typical
analytical methods for the steel. For instance, the chemical composition may be
5 measured by using ICP-AES (Inductively Coupled Plasma-Atomic Emission
Spectrometer: inductively coupled plasma emission spectroscopy spectrometry).
Herein, the acid soluble Al may be measured by ICP-AES using filtrate after heating and
dissolving the sample in acid. In addition, C and S may be measured by the infrared
absorption method after combustion, N may be measured by the thermal conductometric
10 method after fusion in a current of inert gas, and 0 may be measured by, for instance, the
non-dispersive infrared absorption method after fusion in a current of inert gas.
[0048]
Next, conditions for hot-rolling the above steel piece are explained.
The conditions of the hot rolling are not particularly limited. For instance, the
15 conditions are as follows.
The slab is heated before the hot rolling. The slab is put and heated in a known
heating furnace or a known soaking furnace. As one method, the slab is heated to
1280°C or less. By setting the heating temperature of the slab to 1280°C or less, for
instance, it is possible to avoid various problems when the heating temperature is more
20 than 1280°C (a dedicated high temperature heating furnace is required, the melt scale
amount rapidly increases, and the like). The lower limit of the heating temperature of
the slab is not particularly limited. However, when the heating temperature is
excessively low, the hot rolling may become difficult and the productivity may be
decreased. Thus, the heating temperature may be in the range of 1280°C or less in
25 consideration of the productivity. The lower limit of the heating temperature of the slab
21
is preferably 11 00°C. The upper limit of the heating temperature of the slab is
preferably 1250°C.
[0049]
In addition, as another method, the slab is heated to higher temperature of
5 1320°C or more. By heating the slab to higher temperature of 1320°C or more, it is
possible to stabilize the secondary recrystallization by solutionizing AlN and Mn(S, Se)
and by finely precipitating them in the subsequent processes.
10
The slab heating in itself may be omitted, and the hot rolling may be conducted
after casting and before decreasing the temperature of the slab.
[0050]
The heated slab is hot-rolled by a hot rolling mill, and thereby, the hot rolled
steel sheet is obtained. The hot rolling mill includes, for instance, a rough rolling mill
and a final rolling mill which is arranged downstream of the rough rolling mill. The
rough rolling mill includes rough rolling stands which are in a row. Each of the rough
15 rolling stands has plural rolls arranged one above the other. In the same way, the final
rolling mill includes final rolling stands which are in a row. Each of the final rolling
stands has plural rolls arranged one above the other. The heated steel piece is rolled by
the rough rolling mill and then by the final rolling mill, and thereby, the hot rolled steel
sheet is obtained.
20 A final temperature in the hot rolling process (the temperature of the steel sheet
at outlet side of the final rolling stand by which the steel sheet is finally rolled in the final
rolling mill) may be 700 to 1150°C. The hot rolled steel sheet is produced by the hot
rolling process explained above.
[0051]
25 < Hot band annealing process >
5
22
In the hot band annealing process, as necessary, the hot rolled steel sheet
obtained by the hot rolling process is annealed (hot band annealed) to obtain the hot band
annealed sheet. In the embodiment, the steel sheet after the hot band annealing process
is referred to as the hot band annealed sheet.
[0052]
The hot band annealing is conducted in order to homogenize the nonuniform
structure after hot rolling, to control the precipitation of AlN which is the inhibitor
(precipitate finely), and to control secondary phase, solid-soluted carbon, and the like.
As the annealing conditions, known conditions may be applied according to the purpose.
10 For instance, in order to homogenize the nonuniform structure after hot rolling, the hot
rolled steel sheet is hold at 750 to 1200°C of the heating temperature (furnace
temperature in a hot band annealing furnace) for 30 to 600 seconds.
The hot band annealing is not always necessary. The hot band annealing may
be conducted as a result of considering the characteristics and the producing cost required
15 for the grain oriented electrical steel sheet finally produced.
[0053]
< Hot band pickling process >
In the hot band pickling process, as necessary, the hot rolled steel sheet after the
hot rolling process or the hot band annealed sheet after the hot band annealing process in
20 a case where the hot band annealing has been conducted is pickled in order to remove
surface scale. The pickling conditions are not particularly limited, and known
conditions may be appropriate! y applied.
[0054]
< Cold rolling process >
25 In the cold rolling process, the hot rolled steel sheet or the hot band annealed
5
23
sheet after the hot rolling process, the hot band annealing process, or the hot band
pickling process is cold-rolled by once or by plural times with an intermediate annealing
to obtain the cold rolled steel sheet. In the embodiment, the steel sheet after the cold
rolling process is referred to as the cold rolled steel sheet.
[0055]
A cold rolling reduction rate in final cold rolling (cumulative cold rolling
reduction rate without intermediate annealing or cumulative cold rolling reduction rate
after intermediate annealing) is preferably 80% or more, and more preferably 90% or
more. The upper limit of the final cold rolling reduction rate is preferably 95%.
10 [0056]
Herein, the final cold rolling reduction rate(%) is defined as follows.
Final cold rolling reduction rate (%) = ( 1 - Sheet thickness of steel sheet after
final cold rolling I Sheet thickness of steel sheet before final cold rolling ) x 100
[0057]
15 < Decarburization annealing process >
In the decarburization annealing process, the cold rolled steel sheet after the cold
rolling process is subjected to the magnetic domain refining treatment as necessary, and
then, is decarburization -annealed to promote the primary recrystallization. Moreover, in
the decarburization annealing, C which negatively affective in the magnetic
20 characteristics is removed from the steel sheet. In the embodiment, the steel sheet after
the decarburization annealing process is referred to as the decarburization annealed sheet.
[0058]
For the above purposes, in the decarburization annealing, PH20/PH2 which is
the oxidation degree of the atmosphere is to be 0.18 to 0.80, an annealing temperature is
25 to be 750 to 900°C, and a holding is to be 10 to 600 seconds. The oxidation degree
24
PH20/PH2 is defined as the ratio of water vapor partial pressure PH20 (atm) to hydrogen
partial pressure PH2 (atm) in the atmosphere.
[0059]
When the oxidation degree (PH20IPH2) is less than 0.18, dense silicon dioxide
5 (Si02) is quickly formed as an externally oxidized layer, and it is suppressed to release C
outside the system. As a result, the decarburization does not occur properly, and thereby,
the magnetic characteristics after the final annealing deteriorate. On the other hand,
when the oxidation degree is more than 0.80, the oxidized layer of the steel sheet surface
is thickened, and it is difficult to remove the oxidized layer.
10 When the annealing temperature is less than 750°C, the decarburization speed
slows down, and thereby, the productivity decreases. In addition, the decarburization
does not occur properly, and thereby, the magnetic characteristics after the final
annealing deteriorate. On the other hand, when the annealing temperature is more than
900°C, the grain size after the primary recrystallization exceeds favorable size, and
15 thereby, the magnetic characteristics after the final annealing deteriorate.
When the holding time is less than 10 seconds, the decarburization does not
occur sufficient! y, and thereby, the magnetic characteristics after the final annealing
deteriorate. On the other hand, when the holding time is more than 600 seconds, the
grain size after the primary recrystallization exceeds favorable size, and thereby, the
20 magnetic characteristics after the final annealing deteriorate.
[0060]
Depending on the above oxidation degree (PH20/PH2), a heating rate in a
heating stage to the annealing temperature may be controlled. For instance, in a case
where the heating including an induction heating is conducted, an average heating rate
25 may be 5 to 1000 °C/second. Moreover, in a case where the heating including an
25
electric heating is conducted, an average heating rate may be 5 to 3000 °C/second.
[0061]
In addition, in the decarburization annealing process, the nitriding treatment may
be conducted. In the nitriding treatment, the cold rolled steel sheet may be annealed in
5 the atmosphere including ammonia in at least one stage before, during, or after the above
holding. In a case where the temperature for heating the slab is lower, it is preferable
that the nitriding treatment is conducted in the decarburization annealing process. By
additionally conducting the nitriding treatment in the decarburization annealing process,
the inhibitor such as AlN and (Al, Si)N is formed prior to the secondary recrystallization
10 in the final annealing process, and thus, it is possible to make the secondary
recrystallization occur stably.
[0062]
Although the conditions for the nitriding treatment are not particular! y limited, it
is preferable to conduct the nitriding treatment so that the nitrogen content increases by
15 0.003% or more, preferably 0.005% or more, and more preferably 0.007% or more.
20
When the nitrogen (N) content is more than 0.030%, the effects are saturated. Thus, the
nitriding treatment may be conducted so that the nitrogen content becomes 0.030% or
less.
[0063]
The conditions for the nitriding treatment are not particular! y limited, and
known conditions may be appropriate! y applied.
For instance, in a case where the nitriding treatment is conducted after the
holding at 7 50 to 900°C for 10 to 600 seconds in the oxidation degree (PH20/PH2) of
0.01 to 0.15, the nitriding treatment may be conducted such that the cold rolled steel
25 sheet is not cooled to the room temperature but held in the cooling stage in the
26
atmosphere including the ammonia. It is preferable that the oxidation degree
(PH20IPH2) in the cooling stage is within the range of 0.0001 to 0.01. Moreover, in a
case where the nitriding treatment is conducted during the holding at 750 to 900°C for 10
to 600 seconds in the oxidation degree (PH20IPH2) of 0. 01 to 0.15, the ammonia may be
5 included in the atmospheric gas with the above oxidation degree.
[0064]

In the annealing separator applying process, the decarburization annealed sheet
after the decarburization annealing process (or the decarburization annealed sheet after
10 the nitriding treatment) is subjected to the magnetic domain refining treatment as
necessary, and then, the annealing separator is applied to the decarburization annealed
sheet. Thereafter, the applied annealing separator is dried.
The annealing separator mainly includes MgO and further includes MCl which
is at least one selected from the chlorides of the alkali metal, the alkaline earth metal, and
15 Bi. In addition, MCl I MgO which is the mass ratio of MgO and MCl is 2 to 40%.
[0065]
The method for producing the grain oriented electrical steel sheet according to
the embodiment utilizes the annealing separator including MCl which is at least one
selected from the chlorides of the alkali metal, the alkaline earth metal, and Bi. By
20 utilizing the annealing separator including MCl, the forsterite film is not formed due to
the etching ability of MCl included in the the annealing separator during the final
annealing, and thus, the steel sheet with smooth surface is obtained.
[0066]
In the annealing separator, MCl I MgO which is the mass ratio of MgO and MCl
25 is to be 2 to 40%.
27
When MCl I MgO is less than 2%, the formation of the forsterite film may not
be sufficiently suppressed, and coarse Mg based complex oxide may remain. When the
grain oriented electrical steel sheet is deformed, the stress may be locally concentrated in
the Mg based complex oxide, and as a result, the coating adhesion may deteriorate. On
5 the other hand, when MCl I MgO is more than 40%, it may be difficult to remove the
redundant annealing separator in post process.
[0067]
The chlorides of the alkali metal included in the annealing separator are
preferably the chlorides of Li, Na, K, and the like. The chlorides of the alkaline earth
10 metal included in the annealing separator are preferably the chlorides of Ca, Ba, Mg, and
the like. The chlorides of Bi included in the annealing separator may be bismuth
oxychloride (BiOCl), bismuth trichloride (BiCb), and the like.
15
[0068]
< Final annealing process >
The decarburization annealed sheet after applying the above annealing separator
is final-annealed to obtain the final annealed sheet. By conducting the final annealing
for the decarburization annealed sheet after applying the above annealing separator, the
secondary recrystallization proceeds, and the crystal orientation aligns in the { 110}<001>
orientation. In the embodiment, the steel sheet after the final annealing process is
20 referred to as the final annealed sheet.
[0069]
In the final annealing, in a case where the atmosphere (furnace atmosphere)
includes hydrogen, the oxidation degree (PH20IPH2) is to be 0.00010 to 0.2. In a case
where the atmosphere consists of the inert gas (nitrogen, argon, and the like) without the
25 hydrogen, the dew point is to be 0°C or less.
5
28
By controlling the oxidation degree or the dew point to be within the above
range depending on the atmosphere, it is possible to stably proceed the secondary
recrystallization and to increase the alignment degree of the orientation.
[0070]
When the oxidation degree is less than 0.00010 in a case where the atmosphere
includes the hydrogen, the dense surface silica film formed by the decarburization
annealing is reduced before the secondary recrystallization in the final annealing, and
thereby, the secondary recrystallization becomes unstable. On the other hand, when the
oxidation degree is more than 0.2, the dissolution of the inhibitor such as AlN and (Al,
10 Si)N is promoted, and thereby, the secondary recrystallization becomes unstable.
15
Moreover, when the dew point is more than 0°C in a case where the atmosphere consists
of the inert gas without the hydrogen, the dissolution of the inhibitor such as AlN and (Al,
Si)N is promoted, and thereby, the secondary recrystallization becomes unstable. The
lower limit of the dew point is not particularly limited, but may be -30°C for instance.
[0071]
< Annealing separator removing process >
In the annealing separator removing process, the redundant annealing separator
is removed from the surface of the steel sheet after the final annealing (the final annealed
sheet) by methods including one or both of water-washing and pickling. Here, the
20 redundant annealing separator indicates, for instance, the unreacted annealing separator
which has not reacted with the steel sheet during the final annealing.
[0072]
When the redundant annealing separator is not sufficient! y removed from the
surface of the steel sheet, the space factor decreases, and the performance as the iron core
25 deteriorates.
29
[0073]
In order to remove the redundant annealing separator, a scrubber may be utilized
for removing in addition to the water-washing and the pickling. By utilizing the
scrubber, it is possible to reliably remove the redundant annealing separator which
5 deteriorates the wettability in the insulation coating forming process.
[0074]
Moreover, in a case where the pickling is conducted in order to remove the
redundant annealing separator, the pickling may be conducted using the acidic solution
whose volume concentration is less than 20%. For instance, it is preferable to utilize
10 the solution including less than 20 volume% in total of at least one of sulfuric acid, nitric
acid, hydrochloric acid, phosphoric acid, chloric acid, chromium oxide in aqueous
solution, chromate acid mixture, permanganic acid, peroxosulfuric acid, and
peroxophosphoric acid. It is more preferable to utilize the solution including less than
10 volume% thereof. The lower limit of the volume concentration is not particular! y
15 limited, but may be 0.1 volume% for instance. By utilizing the above solution, it is
possible to efficient! y remove the redundant annealing separator from the surface of the
steel sheet. Herein, the above volume% may be the concentration based on the volume
at room temperature.
20
[0075]
Moreover, in a case where the pickling is conducted, the temperature of the
solution is preferably 20 to 80°C. By controlling the temperature of the solution to be
within the above range, it is possible to efficiently remove the redundant annealing
separator from the surface of the steel sheet.
[0076]
25 < Insulation coating forming process >
30
In the insulation coating forming process, the final annealed sheet after the
annealing separator removing process is subjected to the magnetic domain refining
treatment as necessary, and then, the insulation coating is formed on the surface of the
final annealed sheet. In the embodiment, the steel sheet after the insulation coating
5 forming process is referred to as the grain oriented electrical steel sheet.
[0077]
The coating applies the tension to the grain oriented electrical steel sheet, and
thereby, reduces the iron loss as the single steel sheet. Moreover, the coating ensures
interlaminar electrical insulation when the grain oriented electrical steel sheets are
10 utilized after being laminated, and thereby, reduces the iron loss as an iron core.
[0078]
The insulation coating is formed on the surface of the final annealed sheet by
applying the insulation coating forming solution which mainly includes at least one of
the phosphate or the colloidal silica, by baking at 350 to 600°C, and then by heat-treating
15 at 800 to 1000°C.
[0079]
The above phosphate is favorably the phosphate of Ca, Al, Sr, and the like.
Among these, the aluminum phosphate is more preferable. The above colloidal silica is
not particularly limited to the colloidal silica having specific properties. Moreover, the
20 particle size thereof is not particular! y limited to specific particle size, but is preferably
200 nm or less (mean number diameter). For instance, the particle size may be 5 to 30
nm. When the particle size thereof is more than 200 nm, the particles may settle in the
solution. Moreover, the solution may further include the chromic anhydride or the
chromate.
25 [0080]
31
When the baking temperature for the insulation coating is less than 350°C, the
solution for the insulation coating drips during passing the steel sheet, poor appearance is
caused, and the insulation coating with sufficient adhesion is not obtained. When the
baking temperature for the insulation coating is more than 600°C, since the heating rate
5 is excessively fast, only the outermost surface of the insulation coating is solidified, and
the solidification of the inside is delayed, the formation of the coating becomes improper
and the coating adhesion becomes insufficient. When the temperature of the heat
treatment after baking is less than 800°C, the formation of the coating becomes improper
(insufficient solidification), and the coating adhesion becomes insufficient. When the
10 temperature of the heat treatment after baking is more than 1 000°C, the phosphate is
decomposed, the formation of the coating becomes improper, and the coating adhesion
becomes insufficient.
[0081]
In the insulation coating forming, when the oxidation degree (PH20/PH2) of the
15 atmosphere is 0.01 to 1.5, the phosphate is not excessively decomposed, and it is possible
to favorably form the insulation coating.
20
[0082]
The insulation coating forming solution may be applied to the surface of the
steel sheet, for instance, by the wet applying method such as roll coater.
[0083]
< Magnetic domain refining process >
The method for producing the grain oriented electrical steel sheet according to
the embodiment may include the magnetic domain refining process of conducting the
magnetic domain refining treatment at appropriate timing of (first) between the cold
25 rolling process and the decarburization annealing process, (second) between the
5
32
decarburization annealing process and the annealing separator applying process, (third)
between the annealing separator removing process and the insulation coating forming
process, or (fourth) after the insulation coating forming process.
[0084]
By conducting the magnetic domain refining treatment, it is possible to reduce
the iron loss of the grain oriented electrical steel sheet. In a case where the magnetic
domain refining treatment is conducted between the cold rolling process and the
decarburization annealing process, between the decarburization annealing process and
the annealing separator applying process, or between the annealing separator removing
10 process and the insulation coating forming process, the groove may be formed lineally or
15
punctiformly so as to extend in the direction intersecting the rolling direction and so as to
have the predetermined interval in the rolling direction. By forming the above groove,
the width of 180° domain may be narrowed (180° domain may be refined).
[0085]
In a case where the magnetic domain refining treatment is conducted after the
insulation coating forming process, the stress-strain or the groove may be applied or
formed lineally or punctiformly so as to extend in the direction intersecting the rolling
direction and so as to have the predetermined interval in the rolling direction. By
applying the above stress-strain or forming the above groove, the width of 180° domain
20 may be narrowed (180° domain may be refined).
[0086]
The above stress-strain may be applied by irradiating laser beam, electron beam,
and the like. The above groove may be formed by a mechanical groove forming
method such as toothed gear, by a chemical groove forming method such as electrolytic
25 etching, by a thermal groove forming method such as laser irradiation, and the like. In a
5
10
15
33
case where the insulation coating is damaged and the performance such as electrical
insulation deteriorates by applying the above stress-strain or forming the above groove,
the insulation coating may be formed again, and thereby, the damage may be repaired.
[0087]
Fig. 1 shows an instance of the method for producing the grain oriented
electrical steel sheet according to the embodiment. In the figure, the processed
surrounded by the solid line indicates the essential processed, and the processed
surrounded by the broken line indicates the optional processes.
[0088]
The grain oriented electrical steel sheet produced by the method according to the
embodiment does not include the forsterite film. Specifically, the grain oriented
electrical steel sheet includes a base steel sheet, an intermediate layer which is arranged
in contact with the base steel sheet, and the insulation coating which is arranged in
contact with the intermediate layer to be an outermost surface.
[0089]
Whether or not the grain oriented electrical steel sheet includes the forsterite
film may be confirmed by X-ray diffraction method. For instance, the X-ray diffraction
may be conducted for the surface after removing the insulation coating from the grain
oriented electrical steel sheet, and the obtained X-ray diffraction spectrum may be
20 collated with PDF (Powder Diffraction File). The forsterite (Mg2Si04) may be
identified by JCPDS No. 34-189. In the embodiment, when the primal constituent
phase in the above X-ray diffraction spectrum is not the forsterite, the grain oriented
electrical steel sheet is judged not to include the forsterite film.
[0090]
25 In order to only remove the insulation coating from the grain oriented electrical
34
steel sheet, the grain oriented electrical steel sheet with the coating may be immersed in
hot alkaline solution. Specifically, it is possible to remove the insulation coating from
the grain oriented electrical steel sheet by immersing the steel sheet in sodium hydroxide
aqueous solution which includes 30 mass% of NaOH and 70 mass% of H20 at 80°C for
5 20 minutes, washing it with water, and then, drying it. In general, only insulation
coating is removed by the alkaline solution, and the forsterite film is removed by the
acidic solution such as hydrochloric acid.
[0091]
In the grain oriented electrical steel sheet produced by the method according to
10 the embodiment, since the forsterite film is not included, the magnetic characteristics (the
iron loss characteristics) are improved. In addition, since each of the processes is
optimally controlled, the coating adhesion is improved.
15
Examples
[0092]
Hereinafter, the examples of the present invention are explained. However, the
condition in the examples is an example condition employed to confirm the operability
and the effects of the present invention, so that the present invention is not limited to the
example condition. The present invention can employ various types of conditions as
20 long as the conditions do not depart from the scope of the present invention and can
achieve the object of the present invention.
[0093]
In steel slabs having the chemical composition shown in Table 1, the steel slabs
of No. Al3 and No. all were heated to 1350°C, and then hot-rolled to obtain the hot
25 rolled steel sheets having the sheet thickness of 2.6 mm. The hot rolled steel sheets
35
were cold-rolled once or cold-rolled plural times with the intermediate annealing to
obtain the cold rolled steel sheets having the final sheet thickness of 0.22 mm. The cold
rolled steel sheets having the final sheet thickness of 0.22 mm were
decarburization-annealed in the decarburization annealing process under conditions
5 shown in Tables 2 to 4.
[0094]
Moreover, in the steel slabs having the chemical composition shown in Table 1,
the steel slabs except for No. Al3 and No. all were heated to 1150°C, and then
hot-rolled to obtain the hot rolled steel sheets having the sheet thickness of 2.6 mm.
10 The hot rolled steel sheets were cold-rolled once or cold-rolled plural times with the
intermediate annealing to obtain the cold rolled steel sheets having the final sheet
thickness of 0.22 mm. The cold rolled steel sheets having the final sheet thickness of
0.22 mm were decarburization-annealed in the decarburization annealing process under
conditions shown in Tables 2 to 4, and thereafter, the nitriding treatment was conducted
15 during cooling by being held in the atmosphere including the ammonia.
[0095]
In No. B5, the hot rolled steel sheet after the hot rolling was subjected to the hot
band annealing in which the annealing was conducted at 11 oooc and then at 900°C.
Thereafter, the pickling was conducted in order to remove the surface scale, and then, the
20 cold rolling was conducted.
25
[0096]
In the decarburization annealing, the average heating rate in the heating stage to
the annealing temperature was less than 15 °C/second.
[0097]
For the decarburization annealed sheets after the above decarburization
5
10
36
annealing, the annealing separator was applied and dried. The annealing separator
mainly included MgO and included MCl which was the chloride as shown in Tables 2 to
4.
[0098]
The decarburization annealed sheets after applying the annealing separator were
final-annealed at 1100°C or 1200°C for 20 hours. At the time, as shown in Tables 5 to 7,
the oxidation degree was controlled when the atmosphere included the hydrogen (H2),
and the dew point was controlled when the atmosphere did not include the hydrogen.
[0099]
After the final annealing, in the examples of Nos. B8, B10, and B12, the
redundant annealing separator was removed from the steel sheets by water-washing. In
the examples except for Nos. B8, B10, and B12, the redundant annealing separator was
removed by water-washing and thereafter pickling. In the pickling, the steel sheets
were immersed in the sulfuric acid aqueous solution (volume concentration of sulfuric
15 acid : 1 volume%).
[0100]
Thereafter, the insulation coating forming solution which mainly included the
phosphate or the colloidal silica and which included the chromic anhydride as necessary
was applied. In order to form the insulation coating, the above solution was baked at
20 the baking temperature shown in Tables 5 to 7, and then, was heat-treated at the
temperature shown in Tables 5 to 7.
[0101]
Moreover, in the examples, as shown in Tables 8 to 10, the magnetic domain
refining treatment was conducted at any timing of (first) between the cold rolling process
25 and the decarburization annealing process, (second) between the decarburization
37
annealing process and the annealing separator applying process, (third) between the
annealing separator removing process and the insulation coating forming process, or
(fourth) after the insulation coating forming process. For the magnetic domain
refinement, the groove was formed mechanically or chemically, or the stress-strain or the
5 groove was applied or formed by the laser.
[0102]
For the obtained grain oriented electrical steel sheets Nos. B 1 to B44 and b 1 to
b31, the iron loss and the coating adhesion were evaluated.
[0103]
10
The samples were taken from the obtained grain oriented electrical steel sheets,
and the iron loss W17 /50 (W /kg) was measured under the conditions of 50 Hz of AC
frequency and 1. 7 T of excited magnetic flux density on the basis of the epstein test
regulated by JIS C2550-1: 2000. As for the grain oriented electrical steel sheets in
15 which the magnetic domain refinement was conducted, when the iron loss W17 /50 was
less than 0. 7 W /kg, it was judged to as acceptable. As for the grain oriented electrical
steel sheets in which the magnetic domain refinement was not conducted, when the iron
loss W17 /50 was less than 1.0 W /kg, it was judged to as acceptable.
[0104]
20 < Coating adhesion >
The samples were taken from the obtained grain oriented electrical steel sheets,
and the coating adhesion of the insulation coating was evaluated by rolling the sample
around the cylinder with 20 mm of diameter ( 180° bending) and by measuring the area
fraction of remained coating after bending back. In the evaluation of the coating
25 adhesion of the insulation coating, the presence or absence of delamination of the
38
insulation coating was visually evaluated. When the area fraction of remained coating
which was not delaminated from the steel sheet was 90% or more, it was regarded as @
(Very Good). When the area fraction was 85% or more and less than 90%, it was
regarded as o (Good). When the area fraction was 80% or more and less than 85%, it
5 was regarded as L. (Poor). When the area fraction was less than 80%, it was regarded
as x (NG). When the area fraction of remained coating was 85% or more (the above @
and o ), it was judged to as acceptable.
10
The results are shown in Tables 8 to 10.
[0105]
[Table 1]
39
STEEL CHEMICAL COMPOSITION (mass%) (BALANCE CONSISTING OF Fe AND IMPURITIES)
No. c Si Mn s Se S+Se AI N OTHER ELEMENTS
A1 0.030 3.45 0.10 0.006 0.006 0.022 0.008
A2 0.100 3.45 0.10 0.006 0.006 0.022 0.008
A3 0.060 0.80 0.10 0.006 0.006 0.022 0.008
A4 0.060 7.00 0.10 0.006 0.006 0.022 0.008
A5 0.060 3.45 0.01 0.006 0.006 0.022 0.008 Cu : 0.15 .. Ti : 0.006
A6 0.060 3.45 1.00 0.006 0.020 0.026 0.022 0.008 B: 0.002 .. Cr: 0.08 .. V: 0.03
A7 0.060 3.45 0.10 0.004 0.002 0.006 0.022 0.008 P: 0.10., Nb: 0.05
A8 0.060 3.45 0.10 0.050 0.010 0.060 0.022 0.008 Sn: 0.08., Sb: 0.05 .. Ni: 0.05
A9 0.060 3.45 0.10 0.006 0.006 0.010 0.008
A10 0.060 3.45 0.10 0.006 0.006 0.065 0.004
A11 0.060 3.45 0.10 0.006 0.006 0.022 0.012
A12 0.060 3.45 0.10 0.006 0.006 0.022 0.008
A13 0.080 3.25 0.08 0.025 0.001 0.026 0.022 0.007 Bi: 0.004 .. Mo: 0.03
a1 0.010 3.45 0.10 0.006 0.006 0.022 0.008
a2 0.400 3.45 0.10 0.006 0.006 0.022 0.008
a3 0.060 0.50 0.10 0.006 0.006 0.022 0.008
a4 0.060 9.00 0.10 0.006 0.006 0.022 0.008
a5 0.060 3.45 0.004 0.006 0.006 0.022 0.008 Cu: 0.15 .. Ti: 0.006
a6 0.060 3.45 1.50 0.006 0.006 0.022 0.008 B: 0.002 .. Cr: 0.08 .. V: 0.03
a7 0.060 3.45 0.10 0.070 0.070 0.022 0.008 P:0.10 .. Nb:0.05
a8 0.060 3.45 0.10 0.080 0.010 0.090 0.022 0.008 Sn: 0.08 .. Sb: 0.05 .. Ni: 0.05
a9 0.060 3.45 0.10 0.006 0.006 0.005 0.008
a10 0.060 3.45 0.10 0.006 0.006 0.080 0.001
a11 0.060 3.25 0.08 0.025 0.001 0.026 0.022 0.025 Bi: 0.004., Mo: 0.03
[0106]
[Table 2]
40
DECARBURIZATION ANNEALING PROCESS ANNEALING SEPARATOR
APPLYING PROCESS
STEEL OXIDATION ANNEALING HOLDING CHLORIDE MCI/MgO
No. No. DEGREE TEMPERATURE TIME IN
ANNEALING
(-) (oC) (sec) SEPARATOR (mass%)
INVENTIVE 81 A12 0.18 840 60 CaCI2 20
EXAMPLE 82 A12 0.80 840 60 CaCI2 20
83 A12 0.60 750 60 CaCI2 20
84 A12 0.60 900 60 CaCI2 20
85 A12 0.60 840 10 CaCI2 20
86 A12 0.60 840 600 CaCI2 20
87 A12 0.60 840 60 KCI 2
88 A12 0.60 840 60 KCI 40
89 A12 0.60 840 60 CaCI2 2
810 A12 0.60 840 60 CaCI2 40
811 A12 0.60 840 60 8iOCI 2
812 A12 0.60 840 60 8iOCI 40
813 A12 0.60 840 60 CaCI2 20
814 A12 0.60 840 60 CaCI2 20
815 A12 0.60 840 60 CaCI2 20
816 A12 0.60 840 60 CaCI2 20
817 A12 0.60 840 60 CaCI2 20
818 A12 0.60 840 60 CaCI2 20
819 A12 0.60 840 60 CaCI2 20
820 A12 0.60 840 60 CaCI2 20
821 A12 0.60 840 60 CaCI2 20
822 A12 0.60 840 60 CaCI2 20
823 A12 0.60 840 60 CaCI2 20
824 A12 0.60 840 60 CaCI2 20
825 A12 0.60 840 60 CaCI2 20
[0107]
[Table 3]
41
DECARBURIZATION ANNEALING PROCESS ANNEALING SEPARATOR
APPLYING PROCESS
STEEL OXIDATION ANNEALING HOLDING CHLORIDE MCI/MgO
No. No. DEGREE TEMPERATURE TIME IN
ANNEALING
(-) (oC) (sec) SEPARATOR (mass%)
INVENTIVE 826 A12 0.60 840 60 CaCI2 20
EXAMPLE 827 A12 0.60 840 60 CaCI2 20
828 A12 0.60 840 60 CaCI2 20
829 A13 0.60 840 60 CaCI2 20
830 A13 0.60 840 60 CaCI2 20
831 A13 0.60 840 60 CaCI2 20
832 A1 0.60 840 60 CaCI2 20
833 A2 0.60 840 60 CaCI2 20
834 A3 0.60 840 60 CaCI2 20
835 A4 0.60 840 60 CaCI2 20
836 A5 0.60 840 60 CaCI2 20
837 A6 0.60 840 60 CaCI2 20
838 A7 0.60 840 60 CaCI2 20
839 A8 0.60 840 60 CaCI2 20
840 A9 0.60 840 60 CaCI2 20
841 A10 0.60 840 60 CaCI2 20
842 A 11 0.60 840 60 CaCI2 20
843 A12 0.60 840 60 CaCI2 20
844 A12 0.60 840 60 CaCI2 20
COMPARATIVE b1 A12 0.05 840 60 CaCI2 20
EXAMPLE b2 A12 0.98 840 60 CaCI2 20
b3 A12 0.60 600 60 CaCI2 20
b4 A12 0.60 1100 60 CaCI2 20
b5 A12 0.60 840 .Q CaCI2 20
b6 A12 0.60 840 800 CaCI2 20
[0108]
[Table 4]
42
DECARBURIZATION ANNEALING PROCESS ANNEALING SEPARATOR
APPLYING PROCESS
STEEL OXIDATION ANNEALING HOLDING CHLORIDE MCI/MgO
No. No. DEGREE TEMPERATURE TIME IN
ANNEALING
(-) (oC) (sec) SEPARATOR (mass%)
COMPARATIVE b7 A12 0.60 840 60 KCI 1
EXAMPLE b8 A12 0.60 840 60 KCI 50
b9 A12 0.60 840 60 CaCI2 1
b10 A12 0.60 840 60 CaCI2 50
b11 A12 0.60 840 60 BiOCI 1
b12 A12 0.60 840 60 BiOCI 50
b13 A12 0.60 840 60 CaCI2 20
b14 A12 0.60 840 60 CaCI2 20
b15 A12 0.60 840 60 CaCI2 20
b16 A12 0.60 840 60 CaCI2 20
b17 A12 0.60 840 60 CaCI2 20
b18 A12 0.60 840 60 CaCI2 20
b19 A12 0.60 840 60 CaCI2 20
b20 a1 0.60 840 60 CaCI2 20
b21 a2 0.60 840 60 CaCI2 20
b22 a3 0.60 840 60 CaCI2 20
b23 a4 - - - - -
b24 a5 0.60 840 60 CaCI2 20
b25 a6 0.60 840 60 CaCI2 20
b26 a7 0.60 840 60 CaCI2 20
b27 a8 0.60 840 60 CaCI2 20
b28 a9 0.60 840 60 CaCI2 20
b29 a10 0.60 840 60 CaCI2 20
b30 a11 0.60 840 60 CaCI2 20
b31 a10 0.60 840 60 CaCI2 20
[0109]
[Table 5]
~ 0"
I-"'
(D
2J
0
1--'
1--'
8 INVENTIVE
EXAMPLE
STEEL No. No.
81 A12
82 A12
83 A12
84 A12
85 A12
86 A12
87 A12
88 A12
89 A12
810 A12
811 A12
812 A12
813 A12
814 A12
815 A12
816 A12
817 A12
818 A12
819 A12
820 A12
821 A12
822 A12
823 A12
824 A12
825 A12
FINAL ANNEALING PROCESS
ATMOSPHERE TEMPERATURE OXIDATION DEW
DEGREE POINT
(-) oc (-) (oC)
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.0001 -
H2+N2 1200 0.20 -
N2 1200 - -60
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
INSULATION COATING FORMING PROCESS
BAKING HEAT
TEMPERATURE TREATMENT
TEMPERATURE
(oC) (oC)
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 870
400 870
400 870
350 870
600 870
450 800
450 1000
450 850
450 850
450 850
450 850
450 850
450 850
..j:::..
u:;
~ 0"
I-"'
(D
~
0
1--'
1--'
1--' INVENTIVE
EXAMPLE
COMPARATIVE
EXAMPLE
STEEL No. No.
826 A12
827 A12
828 A12
829 A13
830 A13
831 A13
832 A1
833 A2
834 A3
835 A4
836 A5
837 A6
838 A7
839 A8
840 A9
841 A10
842 A 11
843 A12
844 A12
b1 A12
b2 A12
b3 A12
b4 A12
b5 A12
b6 A12
FINAL ANNEALING PROCESS
ATMOSPHERE TEMPERATURE OXIDATION DEW
DEGREE POINT
(-) oc (-) (oC)
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1100 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
N2 1200 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
INSULATION COATING FORMING PROCESS
BAKING HEAT
TEMPERATURE TREATMENT
TEMPERATURE
(oC) (oC)
450 870
400 870
400 850
450 870
400 870
400 850
400 870
400 870
400 870
400 870
400 870
400 870
400 870
400 870
400 870
400 870
400 870
0 400 870
400 870
400 850
400 850
400 850
400 850
400 850
400 850
..j:::..
..j:::..
~ 0"
I-"'
(D
~
0
1--'
1--'
~ COMPARATIVE
EXAMPLE
No.
b7
b8
b9
b10
b11
b12
b13
b14
b15
b16
b17
b18
b19
b20
b21
b22
b23
b24
b25
b26
b27
b28
b29
b30
b31
STEEL
No.
A12
A12
A12
A12
A12
A12
A12
A12
A12
A12
A12
A12
A12
a1
a2
a3
a4
a5
a6
a7
a8
a9
a10
a11
a10
FINAL ANNEALING PROCESS
ATMOSPHERE TEMPERATURE OXIDATION DEW
DEGREE POINT
(-) oc (-) (oC)
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.00008 -
H2+N2 1200 0.50 -
N2 1200 - 1Q
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1100 0.05 -
- - - -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
H2+N2 1200 0.05 -
INSULATION COATING FORMING PROCESS
BAKING HEAT
TEMPERATURE TREATMENT
TEMPERATURE
(oC) (oC)
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
400 850
300 850
800 850
400 700
400 1050
400 870
400 870
400 870
- -
400 870
400 870
400 870
400 870
400 870
400 870
400 870
400 870
..j:::..
Ul
46
MAGNETIC DOMAIN REFINEMENT IRON LOSS COATING
STEEL TIMING FOR METHOD W17/50 ADHESION
No. No. CONTROLLING
(W/kg)
INVENTIVE 81 A12 FOURTH LASER 0.68 0
EXAMPLE 82 A12 FOURTH LASER 0.69 0
83 A12 FOURTH LASER 0.68 0
84 A12 FOURTH LASER 0.68 0
85 A12 FOURTH LASER 0.69 0
86 A12 FOURTH LASER 0.69 0
87 A12 FOURTH LASER 0.68 0
88 A12 FOURTH LASER 0.68 0
89 A12 FOURTH LASER 0.69 0
810 A12 FOURTH LASER 0.69 0
811 A12 FOURTH LASER 0.68 0
812 A12 FOURTH LASER 0.68 0
813 A12 FOURTH LASER 0.68 0
814 A12 FOURTH LASER 0.68 0
815 A12 FOURTH LASER 0.69 0
816 A12 FOURTH LASER 0.69 0
817 A12 FOURTH LASER 0.68 0
818 A12 FOURTH LASER 0.69 0
819 A12 FOURTH LASER 0.68 0
820 A12 FIRST MECHANICAL 0.65 @
GROOVE FORMING
821 A12 SECOND MECHANICAL 0.64 @
GROOVE FORMING
822 A12 THIRD MECHANICAL 0.64 @
GROOVE FORMING
823 A12 FIRST CHEMICAL 0.65 @
GROOVE FORMING
824 A12 SECOND CHEMICAL 0.66 @
GROOVE FORMING
825 A12 THIRD CHEMICAL 0.65 @
GROOVE FORMING
[0113]
[Table 9]
47
MAGNETIC DOMAIN REFINEMENT IRON LOSS COATING
STEEL TIMING FOR METHOD W17/50 ADHESION
No. No. CONTROLLING
(W/kg)
INVENTIVE 826 A12 FOURTH LASER 0.64 @
EXAMPLE 827 A12 FOURTH LASER 0.63 @
828 A12 FOURTH LASER 0.65 @
829 A13 FOURTH LASER 0.64 @
830 A13 FOURTH LASER 0.63 @
831 A13 FOURTH LASER 0.64 @
832 A1 FOURTH LASER 0.68 0
833 A2 FOURTH LASER 0.67 0
834 A3 FOURTH LASER 0.69 0
835 A4 FOURTH LASER 0.68 0
836 A5 FOURTH LASER 0.67 0
837 A6 FOURTH LASER 0.69 0
838 A7 FOURTH LASER 0.67 0
839 A8 FOURTH LASER 0.68 0
840 A9 FOURTH LASER 0.68 0
841 A10 FOURTH LASER 0.69 0
842 A 11 FOURTH LASER 0.67 0
843 A12 FOURTH LASER 0.68 0
844 A12 NO - 0.93 @
COMPARATIVE b1 A12 FOURTH LASER 1.18 ~
EXAMPLE b2 A12 FOURTH LASER 1.09 ~
b3 A12 FOURTH LASER 1.49 ~
b4 A12 FOURTH LASER 1.28 ~
b5 A12 FOURTH LASER 1.15 ~
b6 A12 FOURTH LASER 0.92 ~
[0114]
[Table 10]
48
MAGNETIC DOMAIN REFINEMENT IRON LOSS COATING
STEEL TIMING FOR METHOD W17/50 ADHESION
No. No. CONTROLLING
(W/kg)
COMPARATIVE b7 A12 FOURTH LASER 0.88 X
EXAMPLE b8 A12 FOURTH LASER 1.18 !:::..
b9 A12 FOURTH LASER 0.86 X
b10 A12 FOURTH LASER 1.22 !:::..
b11 A12 FOURTH LASER 0.81 X
b12 A12 FOURTH LASER 1.42 !:::..
b13 A12 FOURTH LASER 0.86 !:::..
b14 A12 FOURTH LASER 0.83 !:::..
b15 A12 FOURTH LASER 0.85 !:::..
b16 A12 FOURTH LASER 0.81 X
b17 A12 FOURTH LASER 0.83 X
b18 A12 FOURTH LASER 0.84 X
b19 A12 FOURTH LASER 0.87 X
b20 a1 FOURTH LASER 0.88 0
b21 a2 FOURTH LASER 0.85 0
b22 a3 FOURTH LASER 0.84 0
b23 a4 - - - -
b24 a5 FOURTH LASER 0.95 0
b25 a6 FOURTH LASER 1.13 0
b26 a7 FOURTH LASER 1.09 0
b27 a8 FOURTH LASER 1.02 0
b28 a9 FOURTH LASER 0.99 0
b29 a10 FOURTH LASER 1.16 0
b30 a11 FOURTH LASER 0.94 0
b31 a10 NO - 1.46 0
[0115]
As shown in Tables 1 to 10, in the inventive examples Nos. B1 to B44, all
process conditions satisfied the range of the present invention, and thus, the iron loss was
5 low. Moreover, the coating adhesion was excellent.
On the other hand, in the comparative examples Nos. b1 to b31, at least one of
the process conditions was out of the range of the present invention, and thus, the iron
loss and/or the coating adhesion was insufficient. Herein, in the comparative example
5
49
No. b23, the rolling could not be conducted, and thus, the evaluation thereafter was not
conducted.
Industrial Applicability
[0116]
According to the above aspects of the present invention, it is possible to provide
the method for producing the grain oriented electrical steel sheet without the forsterite
film and excellent in the magnetic characteristics and the coating adhesion. The
obtained grain oriented electrical steel sheet is excellent in the magnetic characteristics
10 and the coating adhesion, and therefore, the present invention has significant industrial
applicability.
5
10
15
20
25
50
CLAIMS
What is claimed is:
1. A method for producing a grain oriented electrical steel sheet,
the method comprising:
a hot rolling process of hot-rolling a steel piece to obtain a hot rolled steel sheet,
the steel piece including, as a chemical composition, by mass%,
0.030 to 0.100% of C,
0.80 to 7.00% of Si,
0.01 to 1.00% of Mn,
0 to 0.060% in total of S and Se,
0.010 to 0.065% of acid soluble Al,
0.004 to 0.012% ofN,
0 to 0.30% of Cr,
0 to 0.40% of Cu,
0 to 0.50% of P,
0 to 0.30% of Sn,
0 to 0.30% of Sb,
0 to 1.00% ofNi,
0 to 0.008% ofB,
0 to 0.15% ofV,
0 to 0.20% of Nb,
0 to 0.10% ofMo,
0 to 0.015% of Ti,
0 to 0.010% ofBi, and
51
a balance consisting of Fe and impurities;
a cold rolling process of cold-rolling the hot rolled steel sheet to obtain a cold
rolled steel sheet;
a decarburization annealing process of decarburization -annealing the cold rolled
5 steel sheet to obtain a decarburization annealed sheet;
10
15
an annealing separator applying process of applying and drying an annealing
separator including MgO to the decarburization annealed sheet;
a final annealing process of final-annealing the decarburization annealed sheet
after applying the annealing separator to obtain a final annealed sheet;
an annealing separator removing process of removing a redundant annealing
separator from a surface of the final annealed sheet; and
an insulation coating forming process of forming an insulation coating on the
surface of the final annealed sheet,
wherein, in the decarburization annealing process,
PH20/PH2 which is an oxidation degree of an atmosphere is 0.18 to 0.80, an
annealing temperature is 750 to 900°C, and a holding is 10 to 600 seconds,
wherein, in the annealing separator applying process,
the annealing separator further includes MCl which is at least one selected from
chlorides of an alkali metal, an alkaline earth metal, and Bi, and MCl I MgO which is a
20 mass ratio of MgO and MCl is 2 to 40%,
25
wherein, in the final annealing process,
an oxidation degree is 0.00010 to 0.2 when an atmosphere includes a hydrogen,
or a dew point is 0°C or less when an atmosphere consists of an inert gas without a
hydrogen, and
wherein, in the insulation coating forming process,
5
52
the insulation coating is formed by applying an insulation coating forming
solution which mainly includes a phosphate or a colloidal silica, by baking at 350 to
600°C, and then by heat-treating at 800 to 1000°C.
2. The method for producing the grain oriented electrical steel sheet according to
claim 1,
the method including, between the hot rolling process and the cold rolling
process,
at least one of a hot band annealing process of annealing the hot rolled steel
10 sheet or a hot band pickling process of pickling the hot rolled steel sheet.
3. The method for producing the grain oriented electrical steel sheet according to
claim 1 or 2,
wherein, in the decarburization annealing process, a nitriding treatment is
15 conducted by annealing the cold rolled steel sheet in an atmosphere including ammonia.
4. The method for producing the grain oriented electrical steel sheet according to
any one of claims 1 to 3,
the method including, between the cold rolling process and the decarburization
20 annealing process, between the decarburization annealing process and the annealing
separator applying process, between the annealing separator removing process and the
insulation coating forming process, or after the insulation coating forming process,
25
a magnetic domain refining process of conducting a magnetic domain refining
treatment.
53
5. The method for producing the grain oriented electrical steel sheet according to
any one of claims 1 to 4,
wherein, in the annealing separator removing process, a pickling is conducted
after water-washing using an acidic solution whose volume concentration is less than
5 20%.
6. The method for producing the grain oriented electrical steel sheet according to
any one of claims 1 to 5,wherein, the steel piece includes, as the chemical composition, by mass%, at
10 least one selected from a group consisting of
15
20
25
0.02 to 0.30% of Cr,
0.05 to 0.40% of Cu,
0.005 to 0.50% of P,
0.02 to 0.30% of Sn,
0.01 to 0.30% of Sb,
0.01 to 1.00% of Ni,
0.0005 to 0.008% of B,
0.002 to 0.15% ofV,
0.005 to 0.20% of Nb,
0.005 to 0.10% ofMo,
0.002 to 0.015% ofTi, and
0.001 to 0.010% ofBi.