FIELD
[0001]
The present invention relates to a method for producing electrical steel sheet.
10 BACKGROUND
[0002]
Electrical steel sheet is generally classified into grain-oriented electrical steel sheet and nonoriented
electrical steel sheet. Grain-oriented electrical steel sheet is steel sheet which contains Si
in 2 mass% to 5 mass% or so and has grains of the steel sheet integrated in orientation to a high
15 degree to the 110<001> orientation called the “Goss orientation”. Grain-oriented electrical
steel sheet is excellent in magnetic characteristics and, for example, is utilized as the core
material of transformers and other stationary induction apparatus etc. On the other hand, nonoriented
electrical steel sheet, in the case of high grades, in the same way as grain-oriented
electrical steel sheet, contains Si in 2 mass% to 5 mass% or so, but the crystal axis orientations
20 of the crystals are arranged as randomly as possible so that magnetic characteristics leaning
toward any specific orientation of the steel sheet are not exhibited. In the same way as grainoriented
electrical steel sheet, it is excellent in magnetic characteristics and, for example, is
utilized as the core material of the stators and rotors of rotary machines.
[0003]
25 In such electrical steel sheet, various techniques have been developed for improving the
magnetic characteristics. In particular, along with the demands for energy-saving in recent years,
further reduction of the core loss has been sought in electrical steel sheet. Core loss is comprised
of eddy current loss and hysteresis loss.
[0004]
30 For reducing the core loss of grain-oriented electrical steel sheet, raising the degree of
integration of the orientation of the grains of the steel sheet to the Goss orientation to improve
the magnetic flux density and reduce the hysteresis loss is effective.
[0005]
Here, in the production of grain-oriented electrical steel sheet, the crystal orientation is
35 controlled by utilizing the catastrophic grain growth phenomenon called “secondary
recrystallization”. However, to suitably control the crystal orientation by secondary
2
recrystallization, it is important to improve the heat resistance of the microprecipitates in the
steel called “inhibitors”.
[0006]
For example, the method of making the inhibitors completely dissolve at the time of heating
the steel slab before hot rolling, then ma 5 king them finely precipitate in the hot rolling and later
annealing process may be mentioned. Specifically, the method such as illustrated in the
following PTL 1 of using MnS and AlN as inhibitors and rolling by a rolling reduction of more
than 80% in the final cold rolling process or the method such as illustrated in the following PTL
2 of using MnS and MnSe as inhibitors and performing a cold rolling process two times may be
10 mentioned.
[0007]
Further, as explained above, core loss includes eddy current loss. Whether oriented or nonoriented,
by providing the surface of electrical steel sheet with an insulation coating, it becomes
possible to suppress conduction between electrical steel sheets stacked as a core and reduce the
15 eddy current loss of the core and becomes possible to further improve the practical magnetic
characteristics of electrical steel sheet.
Further, to reduce the core loss, the art of subdividing the magnetic domains to reduce the
eddy current loss and as a result lower the core loss is known. This action can also be particularly
applied to grain-oriented electrical steel sheet.
20 [0008]
PTLs 3 and 4 disclose the art of producing grain-oriented electrical steel sheet excellent in
coating characteristics by controlling the conditions of hot rolled annealing and the pickling
treatment conditions. Furthermore, PTL 5 discloses the art of controlling the pickling treatment
conditions, additive conditions of annealing separators, and finish annealing conditions to
25 produce grain-oriented electrical steel excellent in coating characteristics. PTL 6 discloses the art
of improving the coating film adhesion of the insulating coating of non-oriented electrical steel
sheet.
[CITATIONS LIST]
30 [PATENT LITERATURE]
[0009]
[PTL 1] Japanese Examined Patent Publication No. 40-15644
[PTL 2] Japanese Examined Patent Publication No. 51-13469
[PTL 3] Japanese Unexamined Patent Publication No. 2003-193141
35 [PTL 4] Japanese Unexamined Patent Publication No. 2019-99827
[PTL 5] Japanese Unexamined Patent Publication No. 2014-196559
3
[PTL 6] Japanese Unexamined Patent Publication No. 2017-082276
SUMMARY
[TECHNICAL PROBLEM]
5 [0010]
Along with the increasing global regulation of the efficiency of transformers, demand for
reduction of core loss in grain-oriented electrical steel sheet has grown much larger. On the other
hand, transformers are important equipment supporting social infrastructure over the long term,
so continued stable operation is important. For this reason, greater reliability contributing to
10 stabler operation of transformers is being sought from the grain-oriented electrical steel sheet
forming the main members. Further, due to the rising importance of the issue of the global
environment in recent years, in electrical equipment, smaller size, higher output, and higher
energy efficiency have been sought. In the core materials of motors, that is, non-oriented
electrical steel sheets, as well, greater reliability contributing to stabler operation of motors has
15 been demanded.
[0011]
The above PTLs 3 to 5 disclose creating a difference in concentrations of Mn or Cu at the
surface and at the center of thickness as methods for obtaining grain-oriented electrical steel
sheet excellent in magnetic characteristics and/or excellent in coating film adhesion. Further,
20 PTL 6 discloses making Cu and Ni segregate at the surface of the base steel material together
with Sb and Sn as a method for obtaining non-oriented electrical steel sheet excellent in coating
film adhesion. However, sometimes these magnetic characteristics and coating film adhesion
have not been sufficient. Further improvement and ease of manufacture are being demanded.
[0012]
25 Therefore, the present invention was made in consideration of the above problem. An object
of the present invention is to provide a new and improved method for producing electrical steel
sheet enabling production of electrical steel sheet excellent in magnetic characteristics and
coating film adhesion. In this Description, “electrical steel sheet”, unless otherwise indicated,
may be either of grain-oriented electrical steel sheet or non-oriented electrical steel sheet.
30
[SOLUTION TO PROBLEM]
[0013]
To solve the above problem, according to the present invention, the following are provided:
[1] A method for producing electrical steel sheet containing a process of bringing an electrical
35 steel sheet containing, by mass%, C: more than 0% and 0.10% or less, Si: 2.5% or more and
4.5% or less, Mn: 0.01% or more and 5.0% or less, a total of one or more of S, Se, and Te: more
4
than 0% and 0.050% or less, acid soluble Al: more than 0% and 5.0% or less, N: more than 0%
and 0.015% or less, and P: more than 0% and 1.0% or less and having a balance of Fe and
impurities into contact with a solution,
the solution containing one or more elements from among Cu, Hg, Ag, Pb, Cd, Co, Zn, and
Ni, a total of c 5 oncentrations of the elements being 0.00001% or more and 1.0000% or less.
[2] A method for producing electrical steel sheet according to [1], wherein the electrical steel
sheet contains, in place of part of the Fe, one or more elements selected from the group
comprising Cu: 1.0% or less, Sn: 1.0% or less, Ni: 1.0% or less, Cr: 1.0% or less, Sb: 1.0% or
less, and Bi: 1.0% or less.
10 [3] A method for producing electrical steel sheet according to [1] or [2], wherein the process for
bringing the electrical steel sheet into contact with the solution is a pickling process, the pH of
the solution is -1.5 or more and less than 7, the solution temperature is 15C or more and 100C
or less, and the time during which the electrical steel sheet contacts the solution is 5 seconds or
more and 200 seconds or less.
15 [4] A method for producing electrical steel sheet according to any one of [1] to [3], wherein the
process for bringing the electrical steel sheet into contact with the solution is performed at the
hot rolling process or later and before the finish annealing process.
[5] A method for producing electrical steel sheet according to any one of [1] to [4], wherein the
process for bringing the electrical steel sheet into contact with the solution is performed at the
20 finish annealing process or later and before the insulation coating process.
[ADVANTAGEOUS EFFECTS OF INVENTION]
[0014]
According to the present invention, a solution containing one or more elements from among
25 Cu, Hg, Ag, Pb, Cd, Co, Zn, and Ni (in this Description, these will sometimes be referred to as
“Cu etc.”) and the electrical steel sheet are made to contact each other. The electrical steel sheet
includes MnS, MnSe, and MnTe as precipitates (in this Description, these will sometimes be
referred to as “MnS etc.”) MnS and other precipitates act as inhibitors. In the present invention,
if MnS etc. contact a solution containing Cu etc., part of the Mn at the MnS etc., in particular the
30 Mn of the surface layers of the MnS etc., is substituted by Cu etc. By utilizing this phenomenon
to improve the heat resistance of the precipitates, it is possible to improve the inhibitor strength
of the grain-oriented electrical steel sheet and realize high magnetic characteristics.
Further, if bringing steel sheet containing MnS etc. at the surface of the steel sheet into
contact with a solution containing Cu etc., it is possible utilize the phenomenon of Cu and other
35 elements concentrating at the surface of the steel sheet due to the above phenomenon to realize
the manifestation of the effect of control of magnetic domains by the improvement of the thermal
5
conductivity, improvement of the coating film adhesion due to improvement of wettability by the
coating solution, and improvement of the heat removal in stacked cores of transformers or
motors. These effects can be enjoyed not only in grain-oriented electrical steel sheet, but also in
non-oriented electrical steel sheet.
5
DESCRIPTION OF EMBODIMENTS
[0015]
Below, preferred embodiments of the present invention will be explained in detail. Note
that, unless otherwise indicated, the expression “A to B” for the numerical values A and B will
10 mean “A or more and B or less”. If assigning units to only the numerical value B in such an
expression, the units shall also apply to the numerical value A.
[0016]
Method for Producing Electrical Steel Sheet
The inventors discovered the following as a result of intensive study of the method for
15 producing grain-oriented electrical steel sheet for improving adhesion between a coating film
and steel sheet while improving the magnetic characteristics in electrical steel sheet.
[0017]
Specifically, the inventors discovered that if making electrical steel sheet containing MnS
etc. contact a solution containing Cu etc., part of the Mn at the MnS etc., in particular the Mn of
20 the surface layers of the MnS etc., is substituted with Cu etc. and that by making use of this
phenomenon, it is possible to improve the heat resistance of the MnS etc. and thereby improve
the inhibitor strength and improve the magnetic characteristics.
[0018]
Further, they discovered that if bringing electrical steel sheet containing MnS etc. at the
25 surface of the steel sheet into contact with a solution containing Cu etc., it is possible to utilize
the phenomenon of Cu and other elements concentrating at the surface of the steel sheet due to
the above phenomenon to realize the manifestation of the effect of control of magnetic domains
by the improvement of the thermal conductivity of the steel sheet, improvement of the coating
film adhesion due to improvement of wettability by the coating solution, and improvement of the
30 heat removal in stacked cores of transformers or motors.
[0019]
The inventors considered the above discoveries and came up with the present invention. An
embodiment of the present invention is a method for producing electrical steel sheet provided
with the following constitution.
35 [0020]
A method for producing electrical steel sheet containing a process of bringing an electrical
6
steel sheet containing, by mass%, C: more than 0% and 0.10% or less, Si: 2.5% or more and
4.5% or less, Mn: 0.01% or more and 5.0% or less, a total of one or more of S, Se, and Te: more
than 0% and 0.050% or less, acid soluble Al: more than 0% and 5.0% or less, N: more than 0%
and 0.015% or less, and P: more than 0% and 1.0% or less and having a balance of Fe and
5 impurities into contact with a solution,
the solution containing one or more elements from among Cu, Hg, Ag, Pb, Cd, Co, Zn, and
Ni, a total of concentrations of the elements being 0.00001% or more and 1.0000% or less.
[0021]
Below, the method for producing the electrical steel sheet according to the present
10 embodiment will be specifically explained.
[0022]
Chemical Composition of Slab
First, the chemical composition of the electrical steel sheet according to the present
embodiment will be explained. Note that, below, unless otherwise indicated, the expression “%”
15 will be assumed to express “mass%”. Further, the balance other than the elements explained
below consists of Fe and impurities. Here, “impurities” indicate constituents contained in the raw
materials or constituents entering in the process of production which are not intentionally
contained in the steel sheet. Further, the chemical composition of the slab of the material of the
electrical steel sheet is basically based on the composition of the electrical steel sheet. However,
20 in the production of general electrical steel sheet, in particular grain-oriented electrical steel
sheet, part of the contained elements is discharged outside of the system due to the
decarburization annealing and purification annealing in the production process, so the chemical
compositions of the material slab and the final product electrical steel sheet become different.
The slab composition can be suitably adjusted considering the effects of the decarburization
25 annealing and purification annealing in the production process so that the characteristics of the
electrical steel sheet, in particular the grain-oriented electrical steel sheet, become the desired
ones. Further, the expression “electrical steel sheet” in the present invention, unless otherwise
indicated, shall mean electrical steel sheet in any of the processes from the slab to the final
product in the process of production of electrical steel sheet. That is, the expression “electrical
30 steel sheet” in the process of production of present invention, unless otherwise indicated, shall
mean electrical steel sheet in any of the processes from the slab to before the process for coating
the insulation coating in the process of production of electrical steel sheet.
[0023]
The content of C (carbon) is more than 0% and 0.10% or less. C plays various roles, but if C
35 is not contained (if it is 0%), at the time of heating the slab, the grain size becomes excessively
large, whereby the core loss value of the final grain-oriented electrical steel sheet is made to
7
increase, so this is not preferable. If the content of C is more than 0.10%, at the time of
decarburization after cold rolling, the decarburization time becomes long and the production
costs increase, so this is not preferable. Further, if the content of C is more than 0.10%, the
decarburization easily becomes incomplete and there is a possibility of magnetic aging occurring
in the final electrical steel sheet, so this is not 5 preferable. Therefore, the content of C is more
than 0% and 0.10% or less. In the case of production of grain-oriented electrical steel sheet, it is
preferably 0.02% or more and 0.10% or less. More preferably, it is 0.05% or more and 0.09% or
less.
[0024]
10 The content of Si (silicon) is 2.5% or more and 4.5% or less. Si raises the electrical
resistance of the steel sheet to thereby reduce the eddy current loss - which is one of the causes
of core loss. If the content of Si is less than 2.5%, it becomes difficult to sufficiently suppress
eddy current loss of the final electrical steel sheet, so this is not preferable. If the content of Si is
more than 4.5%, the workability of the electrical steel sheet falls, so this is not preferable.
15 Therefore, the content of Si is 2.5% or more and 4.5% or less, preferably 2.7% or more and 4.0%
or less.
[0025]
The content of Mn (manganese) is 0.01% or more and 5.0% or less. Mn forms the inhibitors
MnS, MnSe, MnTe, etc. governing the secondary recrystallization. Further, Mn has the action of
20 increasing the electrical resistance in the same way as Si and reduces the eddy current loss -
which is one of the causes of core loss. If the content of Mn is less than 0.01%, the absolute
amounts of MnS, MnSe, and MnTe causing the secondary recrystallization become insufficient,
so this is not preferable. If the content of Mn is more than 5.0%, at the time of slab heating, the
Mn becomes difficult to dissolve, so this is not preferable. Further, if the content of Mn is more
25 than 5.0%, the precipitated size of the inhibitors MnS, MnSe, and MnTe easily becomes coarser
and the optimal distribution of size as inhibitors is detracted from, so this is not preferable.
Therefore, the content of Mn is 0.01% or more and 5.0% or less, In the case of production of
grain-oriented electrical steel sheet, it is preferably 0.01% or more and 0.50% or less, more
preferably 0.01% or more and 0.30% or less, still more preferably 0.03% or more and 0.15% or
30 less. It may be made the above content from the viewpoint of reduction of the core loss (eddy
current loss) as well.
[0026]
The total content of the one or more elements from among S (sulfur), Se (selenium), and Te
(tellurium) is a total of more than 0% and 0.050% or less. S, Se, and Te form inhibitors together
35 with the above-mentioned Mn. All of the three of S, Se, and Te may be included in the electrical
steel sheet, but it is sufficient that at least one of any of them be contained in the electrical steel
8
sheet. If the total of the contents of S, Se, and Te is outside the above range, a sufficient inhibitor
effect cannot be obtained, so this is not preferable. However, in the case of non-oriented
electrical steel sheet, inhibitors are unnecessary, so the less the better. 0% is preferable, but
rendering the content 0% sometimes requires higher costs, so the content is made more than 0%.
Further, if more than the above upper limit, 5 MnS and other sulfides precipitate in large amounts
and the increase in core loss becomes remarkable. Therefore, the content of one or more
elements among S, Se, and Te is a total of more than 0% and 0.050% or less, preferably 0.001%
or more and 0.040% or less.
[0027]
10 The content of acid soluble Al (acid soluble aluminum) is more than 0% and 5.0% or less.
The acid soluble Al forms the inhibitors (AlN) useful for producing high magnetic flux density
electrical steel sheet, in particular grain-oriented electrical steel sheet. Further, Al has the action
of increasing the electrical resistance in the same way as Si and reduces the eddy current loss -
one of the causes of core loss. If the content of acid soluble Al is 0, sometimes no AlN is present,
15 the inhibitor strength becomes insufficient, and good magnetic characteristics cannot be
obtained, so this is not preferable. If the content of acid soluble Al is more than 5.0%, the AlN
precipitating as inhibitors becomes coarser and causes the inhibitor strength to drop, so this is not
preferable. Therefore, the content of acid soluble Al is more than 0% and 5.0% or less, in the
case of production of grain-oriented electrical steel sheet, preferably more than 0% and 0.05% or
20 less, more preferably more than 0% and 0.04% or less.
[0028]
The content of N (nitrogen) is more than 0% and 0.015% or less. N forms the inhibitor AlN
together with the above-mentioned acid soluble Al. If the content of N is outside the above
range, a sufficient inhibitor effect cannot be obtained and sometimes good magnetic
25 characteristics cannot be obtained, so this is not preferable. Further, if more than the above upper
limit, the increase in core loss becomes remarkable due to the increase in nitrides. Therefore, the
content of N is more than 0% and 0.015% or less, preferably more than 0% and 0.012% or less.
[0029]
The content of P (phosphorus) is more than 0% and 1.0% or less. P has the action of raising
30 the strength without causing a drop in the magnetic flux density. However, if causing P to be
excessively contained, the toughness of the steel becomes impaired and the steel sheet easily
breaks. For this reason, the upper limit of the amount of P is made 1.0%. Preferably it is 0.150%
or less, more preferably 0.120% or less. The lower limit of the amount of P is not particularly
limited, but if considering the production costs, it becomes 0.001% or more.
35 [0030]
Further, the slab used for the production of electrical steel sheet according to the present
9
embodiment, in particular grain-oriented electrical steel sheet, may contain one or more elements
of any of Cu, Sn, Ni, Cr, Sb, or Bi as elements stabilizing the secondary recrystallization in
individual contents of 0% or more and 1.0% or less in addition to the above-mentioned elements.
The contents of these elements are preferably individual contents of 0.0005% or more and
0.3000% or less. If the slab contains the above 5 elements, the magnetic flux density of electrical
steel sheet produced, in particular grain-oriented electrical steel sheet, can be further improved.
[0031]
The slab is formed by casting molten steel adjusted so that the electrical steel sheet becomes
the chemical composition explained above. Note that, the method of casting the slab is not
10 particularly limited. Further, in R&D, even if a steel ingot is formed by a vacuum melting
furnace etc., a similar effect as the case where the slab is formed for the above constituents can
be confirmed.
[0032]
Process for Forming Hot Rolled Steel Sheet
15 Next, the slab is heated and hot rolled to work it into a hot rolled steel sheet. The slab
heating temperature is not particularly limited. If making the inhibitor constituents in the slab
completely dissolve, for example, it may be heated to 1280C or more. Note that, the upper limit
value of the heating temperature of the slab at this time is not particularly prescribed, but from
the viewpoint of protection of the facilities, 1450C is preferable. For example, the heating
20 temperature of the slab may be 1280C or more and 1450C or less. On the other hand, if not
making the inhibitor constituents in the slab completely dissolve, for example, the heating
temperature of the slab may be less than 1280C. In this case, the steel sheet may also be nitrided
in any process from the hot rolled annealing process to the finish annealing process. Further, in
the case of non-oriented electrical steel sheet, at the time of slab heating, the S compounds, N
25 compounds, etc. redissolve, but to avoid their subsequent fine precipitation and deterioration of
the magnetic characteristics, the usual slab heating temperature may be 1150C or less,
preferably 1100C or less, more preferably 1050C or less.
[0033]
Next, the heated slab is hot rolled to work it to hot rolled steel sheet. The thickness of the
30 worked hot rolled steel sheet may, for example, be 1.8 mm or more and 3.5 mm or less. If the
thickness of the hot rolled steel sheet is less than 1.8 mm, sometimes the shape of the steel sheet
after hot rolling becomes poor, so this is not preferable. If the thickness of the hot rolled steel
sheet is more than 3.5 mm, the rolling load in the process of cold rolling becomes larger, so this
is not preferable.
35 [0034]
Process for Forming Cold Rolled Steel Sheet
10
Next, the obtained hot rolled steel sheet is annealed, then is worked into a cold rolled sheet
by a single cold rolling operation or several cold rolling operations with process annealing
interposed. Note that, if rolling by a plurality of cold rolling operations with process annealing
interposed, it is also possible to omit the previous stage hot rolled annealing. However, if
annealing the hot rolled sheet, the shape 5 of the steel sheet becomes better, so it is possible to
reduce the possibility of the steel sheet breaking due to cold rolling. Note that, before being sent
to cold rolling, it is preferable to perform pickling to remove the scale etc. deposited on the
surface of the steel sheet. For control of the inhibitors in the thickness direction explained later,
pickling need only be performed at least once at the hot rolling or later and before the primary
10 recrystallization annealing. If rolling by a plurality of cold rolling operations, from the viewpoint
of reducing roll wear in cold rolling, it is preferable to perform the pickling treatment before the
individual cold rolling processes.
[0035]
Further, the steel sheet may be heat treated at 300C or so or less between passes of cold
15 rolling, between rolling stands, or during rolling. In such a case, the magnetic characteristics of
the final grain-oriented electrical steel sheet can be improved. Note that, the hot rolled steel sheet
may be rolled by cold rolling three times or more, but a large number of cold rolling operations
increases the production costs, so the hot rolled steel sheet is preferably rolled by one or two cold
rolling operations. If performing the cold rolling by Sendzimir or other reverse rolling, the
20 number of passes in the cold rolling operations is not particularly limited, but from the viewpoint
of production costs, nine passes or less is preferable.
[0036]
Process of Making Electrical Steel Sheet Contact Solution
The method for producing the electrical steel sheet of the present invention is characterized
25 by making the electrical steel sheet contact a solution containing one or more elements from
among Cu, Hg, Ag, Pb, Cd, Co, Zn, and Ni (in the present Description, these sometimes being
referred to as the “Cu etc.”) and having a total of concentrations of the elements of 0.00001% or
more and 1.0000% or less (in the present Description, sometimes referred to as the “solution
contact treatment” or “solution contact process”).
30 [0037]
The electrical steel sheet contains MnS, MnSe, and MnTe (in the present Description, these
sometimes being referred to as “MnS etc.”) as precipitates. These precipitates act as inhibitors. In
the present invention, if MnS etc. contact a solution containing Cu etc., part of the Mn in the
MnS etc., in particular the Mn at the surface layers of the MnS etc., is substituted by the Cu etc.
35 By improving the heat resistance of the precipitates by this phenomenon, it is possible to
improve the inhibitor strength of the grain-oriented electrical steel sheet and realize high
11
magnetic characteristics.
Further, it is possible to utilize the phenomenon of Cu and other elements concentrating at
the surface of the steel sheet by this phenomenon to realize manifestation of the effect of control
of magnetic domains by improvement of the thermal conductivity, improvement of the coating
film adhesion by improvement of the wettability 5 of the coating solution, and improvement of
heat removal in stacked cores of transformers and motors. These effects can be enjoyed not only
in grain-oriented electrical steel sheet, but also in non-oriented electrical steel sheet.
[0038]
The mechanism by which control of the inhibitors in the thickness direction becomes
10 possible by making a solution containing Cu etc. contact electrical steel sheet is presumed to be
as follows: If making the solution contain one or more elements from among Cu, Hg, Ag, Pb,
Cd, Co, Zn, and Ni, since these elements are extremely high in affinity with the S, Se, and Te in
the solution, they substitute the Mn of the MnS, MnSe, and MnTe precipitates exposed at the
surface of the steel sheet and form compounds. This reaction easily occurs at the MnS and other
15 precipitates, in particular the surface sides contacting the solution. It is believed that if Mn is
substituted by other metal elements (Cu etc.) at the surface sides of the MnS and other
precipitates, these surface side compounds act as barriers keeping the Mn and S, Se, and Te at
the center sides of the MnS and other precipitates from dissolving into the steel, so Ostwald
ripening of the MnS etc. at the finish annealing process is suppressed and the heat resistance of
20 the MnS and other precipitates, that is, the inhibitor strength, rises. This reaction occurs if a
solution containing one or more elements from among Cu, Hg, Ag, Pb, Cd, Co, Zn, and Ni
contacts the MnS, MnSe and MnTe. Therefore, it is believed that if there are cracks, voids, or
other defects at the surface layer of the steel sheet, the solution passes through these spaces to
infiltrate the steel sheet and reacts with not only the MnS etc. exposed at the surface-most part of
25 the steel sheet, but also the MnS etc. in a range of a certain depth of the surface layer of the steel
sheet to raise the inhibitor strength. Before the solution contact of the electrical steel sheet, it is
also possible to perform shot blasting treatment etc. to introduce cracks and other defects to the
surface of the steel sheet for the purpose of raising the inhibitor strength of MnS etc. in the range
of a certain depth. Further, in addition to the rise in the heat resistance, that is, inhibitor strength,
30 explained above, it is possible to use the concentrated Cu and other elements to realize the
manifestation of the effect of control of magnetic domains by the improvement of the thermal
conductivity, improvement of the coating film adhesion due to improvement of wettability by the
coating solution, and improvement of the heat removal in stacked cores of transformers or
motors.
35 [0039]
If the total of the one or more elements among the Cu, Hg, Ag, Pb, Cd, Co, Zn, and Ni of
12
the solution is less than 0.00001%, the effect of control of the inhibitors in the thickness
direction and the effects resulting from concentration of Cu etc. such as the manifestation of the
effect of control of the magnetic domains, improvement of the coating film adhesion, and
improvement of heat removal become insufficient, so this is not preferable. If the total of the one
or more elements among 5 the Cu, Hg, Ag, Pb, Cd, Co, Zn, and Ni of the solution is more than
1.0000%, the effect of improvement of the magnetic characteristics becomes saturated, so this is
not preferable. Therefore, the total of the one or more elements among the Cu, Hg, Ag, Pb, Cd,
Co, Zn, and Ni of the solution is 0.00001% or more and 1.0000% or less.
[0040]
10 Further, in general, the pH of the solution is preferably lower. A solution with a low pH has
a pickling effect. It is believed that the solution reacts with not only the MnS etc. exposed at the
surface-most part of the steel sheet, but also the MnS etc. in a range of a certain depth of the
surface layer of the steel sheet so as to raise the inhibitor strengthening and further promote the
concentration of Cu etc. However, if the pH of the solution is less than -1, the acidity becomes
15 too strong and handling of the solution becomes difficult, so this is not preferable. If the pH of
the solution is 7 or more, sometimes the effect of the pickling treatment is not sufficiently
obtained and the effect of control of the inhibitors in the thickness direction becomes
insufficient. Therefore, the pH of the solution may be made -1.5 or more and less than 7. The
lower the pH of the solution, the higher the pickling effect and the more strengthening by the
20 inhibitors is promoted, so the pH of the solution is preferably -1.5 or more and 6 or less, more
preferably ‐1.5 or more and 5 or less. Note that, as the acid constituent which the solution
contains, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc. may be illustrated.
[0041]
Further, if the temperature of the solution is less than 15C, the effect of the pickling
25 treatment cannot be sufficiently obtained and sometimes the effect of control of the inhibitors in
the thickness direction becomes insufficient. If the temperature of the solution is more than
100C, sometimes handling of the solution becomes difficult. Therefore, the temperature of the
solution may be made 15C or more and 100C or less.
[0042]
30 Further, if the time during which the steel sheet contacts the solution is less than 5 seconds,
the contact time is not sufficient and sometimes the effects of the pickling and inhibitor
strengthening and the Cu concentration etc. become insufficient. If the time during which the
steel sheet contacts the solution is more than 200 seconds, the facilities for causing contact
become long and large, so this is not preferable. Therefore, the time during which the steel sheet
35 contacts the solution may be made 5 seconds or more and 200 seconds or less.
[0043]
13
Therefore, the process of making the electrical steel sheet contact a solution (solution
contact process) may be a pickling process. The above pH value, solution temperature, and
contact time (pickling time) may be employed as the pickling conditions. In general, in the
process of production of steel sheet, pickling treatment is performed before the later processes
for the purpose of removing scale, cleaning the surface 5 of the steel sheet, etc. Typically, from the
viewpoint of decreasing roll wear in cold rolling, the pickling treatment may also be performed
before the individual cold rolling processes. Further, from the viewpoint of controlling the
oxidation of the surface of the steel sheet in the primary recrystallization annealing, the pickling
treatment may also be applied before the primary recrystallization annealing. Furthermore, from
10 the viewpoint of improvement of the coatability of the annealing separator, the pickling
treatment may also be applied before the finish annealing. In particular, from the viewpoint of
improving the coatability of the insulation coating, the pickling treatment may be applied before
the flattening annealing. These pickling treatments may also be applied combined.
Note that, the effect of improvement of the heat resistance of the inhibitors (precipitates) due
15 to the present art etc. can also be obtained in application to other types of steel. For example,
they may also be applied to non-oriented electrical steel sheet. In the case of application to other
types of steel, the slab constituents and process conditions are not limited to the above.
[0044]
Method for Confirming Surfaces of “MnS Etc.” Precipitates Substituted by “Cu Etc.”
20 The method for confirming that the surfaces of the MnS and other precipitates are
substituted by Cu etc. will be explained.
First, the steel sheet sample to be confirmed is polished to a mirror finish and examined by
an SEM-EDX. In the observed image obtained by the SEM, the presence of MnS and other
precipitates can be confirmed. At the examined image, element mapping of EDX of the Cu etc.,
25 for example, Mn, S, and Cu, and the strength ratio are superposed. Due to this, it is possible to
confirm the constituent elements of the precipitate particles. In a typical example, if examining
the precipitate particles and their vicinities, the mapping strength ratio of the Mn and S rises at
the parts of the precipitate particles, so it can be confirmed that the particles are MnS particles.
Furthermore, if the mapping strength ratio of Cu also rises at the part near the surface of the
30 particles, it is presumed that the surface of the precipitates is substituted by Cu.

CLAIMS
[Claim 1]
A method for producing electrical steel sheet containing a process of bringing an electrical
steel sheet containing, by mass%, C: more 5 than 0% and 0.10% or less, Si: 2.5% or more and
4.5% or less, Mn: 0.01% or more and 5.0% or less, a total of one or more of S, Se, and Te: more
than 0% and 0.050% or less, acid soluble Al: more than 0% and 5.0% or less, N: more than 0%
and 0.015% or less, and P: more than 0% and 1.0% or less and having a balance of Fe and
impurities into contact with a solution,
10 the solution containing one or more elements from among Cu, Hg, Ag, Pb, Cd, Co, Zn, and
Ni, a total of concentrations of the elements being 0.00001% or more and 1.0000% or less.
[Claim 2]
A method for producing electrical steel sheet according to claim 1, wherein the electrical
15 steel sheet contains, in place of part of the Fe, one or more elements selected from the group
comprising Cu: 1.0% or less, Sn: 1.0% or less, Ni: 1.0% or less, Cr: 1.0% or less, Sb: 1.0% or
less, and Bi: 1.0% or less.
[Claim 3]
20 A method for producing electrical steel sheet according to claim 1 or 2, wherein the process
for bringing the electrical steel sheet into contact with the solution is a pickling process, the pH
of the solution is -1.5 or more and less than 7, the solution temperature is 15C or more and
100C or less, and the time during which the electrical steel sheet contacts the solution is 5
seconds or more and 200 seconds or less.
25
[Claim 4]
A method for producing electrical steel sheet according to any one of claims 1 to 3, wherein
the process for bringing the electrical steel sheet into contact with the solution is performed at
the hot rolling process or later and before the finish annealing process.
30
[Claim 5]
A method for producing electrical steel sheet according to any one of claims 1 to 4, wherein
the process for bringing the electrical steel sheet into contact with the solution is performed at
the finish annealing process or later and before the insulation coating process.