NON-ORIENTED ELECTRICAL STEEL SHEET AND METHOD OF PRODUCING SAME

Information

  • Patent Application
  • 20250101542
  • Publication Number
    20250101542
  • Date Filed
    January 20, 2023
    2 years ago
  • Date Published
    March 27, 2025
    a month ago
Abstract
Provided is a non-oriented electrical steel sheet with low high-frequency iron loss without addition of a large amount of alloying elements such as Cr, which causes a decrease in magnetic flux density, and without reduction of the sheet thickness, which causes a decrease in productivity. A non-oriented electrical steel sheet comprises a certain chemical composition containing 0.0005 mass % to 0.0050 mass % of Co, wherein at at least one surface of the non-oriented electrical steel sheet, an amount of N existing as AlN in a range from the surface to a depth of 1/20 of a thickness of the non-oriented electrical steel sheet is 0.003 mass % or less, and the surface has an oxide layer containing one or both of Al and Si and having a thickness of 80 nm to 200 nm.
Description
TECHNICAL FIELD

The present disclosure relates to a non-oriented electrical steel sheet and a method of producing the same.


BACKGROUND

In recent years, energy saving is required due to consideration for the environment such as global warming. In the automotive field, hybrid electric vehicles (HEVs) that use both an engine and a motor, electric vehicles (EVs) driven only by an electric motor, fuel cell electric vehicles (FCEVs), etc. are being developed. The motors used in these vehicles are typically driven in a high frequency range which is advantageous for high speed rotation, in order to enhance efficiency. Non-oriented electrical steel sheets are often used as an iron core material for such drive motors of HEVs and EVs. In order to achieve high motor efficiency, non-oriented electrical steel sheets are strongly required to have lower iron loss in the high frequency range.


Conventionally, the iron loss of non-oriented electrical steel sheets is reduced mainly by adding alloying elements such as Si and Al to enhance specific resistance or by reducing the sheet thickness to reduce eddy current loss. However, when a large amount of alloying elements are added for iron loss reduction, saturation magnetic flux density decreases. A decrease in magnetic flux density causes an increase in copper loss in the motor, leading to lower motor efficiency. Moreover, in order to reduce the thickness of the non-oriented electrical steel sheet, it is necessary to reduce the thickness of the hot-rolled steel sheet or increase the cold rolling reduction in the production process. This lowers productivity.


Accordingly, if a non-oriented electrical steel sheet that has both high magnetic flux density and low iron loss in the high frequency range and also has excellent productivity can be developed, it will greatly contribute to higher efficiency of electric devices.


As a method of achieving low iron loss in the high frequency range, for example, JP H11-343544 A (PTL 1) discloses a method in which 1.5 mass % to 20 mass % of Cr is added to enhance the specific resistance of steel and achieve low iron loss in the high frequency range.


CITATION LIST
Patent Literature



  • PTL 1: JP H11-343544 A



SUMMARY
Technical Problem

However, since Cr is an element that decreases saturation magnetic flux density, the technique disclosed in PTL 1, which requires the addition of a large amount of Cr, cannot achieve both high magnetic flux density and low high-frequency iron loss.


It could therefore be helpful to provide a non-oriented electrical steel sheet with reduced iron loss in a high frequency range without addition of a large amount of alloying elements such as Cr, which causes a decrease in magnetic flux density, and without reduction of the sheet thickness, which causes a decrease in productivity.


Solution to Problem

Upon careful examination focusing on the influence of the surface state of a non-oriented electrical steel sheet on its magnetic properties, we discovered that, by limiting the Co content in the steel to a certain range and subjecting the steel sheet after final annealing to acidizing to limit the nitrogen amount in the surface layer to a certain range, iron loss can be reduced without causing a decrease in magnetic flux density.


The present disclosure is based on these discoveries. We thus provide the following.


1. A non-oriented electrical steel sheet comprising a chemical composition containing (consisting of), in mass %, C: 0.0050% or less, Si: 2.0% to 6.5%, Mn: 0.05% to 2.0%, P: 0.10% or less, S: 0.0050% or less, Al: 0.3% to 3.0%, N: 0.0050% or less, Co: 0.0005% to 0.0050%, Ti: 0.0030% or less, Nb: 0.0030% or less, and O: 0.0050% or less, with a balance consisting of Fe and inevitable impurities, wherein at at least one surface of the non-oriented electrical steel sheet, an amount of N existing as AlN in a range from the surface to a depth of 1/20 of a thickness of the non-oriented electrical steel sheet is 0.003 mass % or less, and the surface has an oxide layer containing one or both of Al and Si and having a thickness of 80 nm to 200 nm.


2. The non-oriented electrical steel sheet according to 1., wherein a Si concentration in the oxide layer is 12 at % or more.


3. The non-oriented electrical steel sheet according to 1, or 2., wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F:

    • group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,
    • group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,
    • group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,
    • group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,
    • group E: Zn: 0.001% to 0.05%, and
    • group F: one or both of Mo and W: 0.001% to 0.05% in total.


4. A method of producing a non-oriented electrical steel sheet, the method comprising: subjecting a steel material to cold rolling once or twice or more with intermediate annealing therebetween to obtain a cold-rolled steel sheet, the steel material having a chemical composition containing, in mass %, C: 0.0050% or less, Si: 2.0% to 6.5%, Mn: 0.05% to 2.0%, P: 0.10% or less, S: 0.0050% or less, Al: 0.3% to 3.0%, N: 0.0050% or less, Co: 0.0005% to 0.0050%, Ti: 0.0030% or less, Nb: 0.0030% or less, and O: 0.0050% or less, with a balance consisting of Fe and inevitable impurities; subjecting the cold-rolled steel sheet to final annealing to produce a non-oriented electrical steel sheet; and subjecting, after the final annealing, a surface of the steel sheet to acidizing for 1 second to 60 seconds using an acid containing at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid at a total concentration of 3 wt % to 30 wt %.


5. The method of producing a non-oriented electrical steel sheet according to 4., comprising: subjecting, before the cold rolling, the steel material to hot rolling to obtain a hot-rolled steel sheet; and subjecting the hot-rolled steel sheet to hot-rolled sheet annealing to obtain a hot-rolled and annealed sheet, wherein the hot-rolled and annealed sheet is subjected to the cold rolling.


6. The method of producing a non-oriented electrical steel sheet according to 4, or 5., wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F:

    • group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,
    • group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,
    • group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,
    • group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,
    • group E: Zn: 0.001% to 0.05%, and
    • group F: one or both of Mo and W: 0.001% to 0.05% in total.


Advantageous Effect

It is thus possible to provide a non-oriented electrical steel sheet with reduced iron loss in a high frequency range without causing a decrease in magnetic flux density or productivity. In detail, since low high-frequency iron loss can be achieved by adding a small amount of Co and controlling the nitrogen amount in the surface layer by acidizing, addition of a large amount of alloying elements such as Cr, which causes a decrease in magnetic flux density, is unnecessary. Moreover, excellent magnetic properties can be achieved without reduction of the sheet thickness, which causes a decrease in productivity.





BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:



FIG. 1 is a graph illustrating the correlation between Co content and high-frequency iron loss (W10/400);



FIG. 2 is a graph illustrating the correlation between surface layer nitridation amount and high-frequency iron loss (W10/400);



FIG. 3 is a graph illustrating the correlation between acid concentration and high-frequency iron loss (W10/400);



FIG. 4 is a graph illustrating the correlation between acid concentration and surface layer nitridation amount;



FIG. 5 is a graph illustrating the correlation between acidizing time and high-frequency iron loss (W10/400); and



FIG. 6 is a graph illustrating the correlation between acidizing time and surface layer nitridation amount.





DETAILED DESCRIPTION

First, experiments that led to development of the presently disclosed techniques will be described. In the specification, “%” as a unit of content refers to “mass %” unless otherwise specified. The unit of acid concentration is “wt %”.


<Experiment 1>

A plurality of non-oriented electrical steel sheets with different Co contents were each produced according to the following procedure, and the iron loss in the high frequency range of each of the obtained non-oriented electrical steel sheets was evaluated.


Steel containing C: 0.0023%, Si: 3.2%, Mn: 0.7%, P: 0.01%, S: 0.0018%, Al: 0.8%, N: 0.0019%, Ti: 0.0012%, Nb: 0.0006%, O: 0.0022%, and Co: 0.0001% to 0.01% with the balance consisting of Fe and inevitable impurities was obtained by steelmaking in a vacuum furnace and cast into a steel ingot. The steel ingot was hot rolled to obtain a hot-rolled steel sheet with a sheet thickness of 2.0 mm, and the hot-rolled steel sheet was subjected to hot-rolled sheet annealing at 950° C. for 30 seconds to obtain a hot-rolled and annealed sheet. The hot-rolled and annealed sheet was pickled and then cold rolled to obtain a cold-rolled steel sheet with a final sheet thickness of 0.25 mm.


The obtained cold-rolled steel sheet was subjected to final annealing at 1000° C. for 10 seconds in an atmosphere of H2: N2=10:90 in vol %, and then subjected to acidizing. In the acidizing, the steel sheet was immersed in 10% hydrochloric acid for 10 seconds.


Test pieces of 30 mm in width and 180 mm in length were cut out from the rolling direction (L direction) and transverse direction (C direction) of the non-oriented electrical steel sheet obtained in the foregoing manner, and the high-frequency iron loss of the test pieces was evaluated. Specifically, the iron loss W10/400 of the test pieces in the (L+C) direction at a maximum magnetic flux density of 1.0 T and a frequency of 400 Hz was measured by Epstein testing. FIG. 1 illustrates the correlation between the Co content and the measured W10/400.


As can be seen from the results illustrated in FIG. 1, the iron loss decreased significantly when the Co content was in the range of 0.0005% to 0.0050%.


In order to investigate the cause of the decrease in iron loss by the addition of a small amount of Co, a section in the rolling direction of each non-oriented electrical steel sheet produced in the above experiment was observed using a scanning electron microscope (SEM). As a result, in each non-oriented electrical steel sheet having a Co content outside the range of 0.0005% to 0.0050%, precipitation of fine AlN was observed in the range from the surface of the steel sheet to a depth of 1/20 of the sheet thickness (hereafter also referred to as “surface layer”). In each non-oriented electrical steel sheet having a Co content in the range of 0.0005% to 0.0050%, on the other hand, AlN hardly precipitated in the surface layer.


Typically, in the production process of a non-oriented electrical steel sheet, nitrogen in the atmosphere diffuses into the steel sheet during final annealing, resulting in the formation of nitrides such as AlN in the surface layer (such a surface layer into which nitrides have precipitated is also referred to as “nitrided layer”). However, the above experimental results suggest that, in each non-oriented electrical steel sheet having a Co content in the range of 0.0005% to 0.0050%, the amount of nitrides (AlN) in the surface layer was reduced for some reason and consequently the iron loss decreased.


Then, the concentration of N existing as AlN in the range from the surface of the non-oriented electrical steel sheet to a depth of 1/20 of the sheet thickness (hereafter referred to as “surface layer nitridation amount”) was analyzed by electrolytic extraction. FIG. 2 illustrates the correlation between the measured surface layer nitridation amount and W10/400.


As can be seen from the results illustrated in FIG. 2, there was a strong correlation between the surface layer nitridation amount and the iron loss. In particular, the iron loss decreased significantly when the surface layer nitridation amount was 0.003% or less. Thus, the iron loss decreased as a result of reduction in the amount of AlN, as mentioned above. In all steel sheets having a surface layer nitridation amount of 0.003% or less, the Co content was in the range of 0.0005% to 0.0050%.


Further, the surface of each non-oriented electrical steel sheet that was found to have decreased in iron loss was observed using a transmission electron microscope (TEM). The observation revealed that the nitrided layer at the surface of the steel sheet had been removed and instead an oxide layer containing one or both of Al and Si and having a thickness of 80 nm to 200 nm had been formed.


From these experimental results, the reason why the iron loss decreased in each steel sheet containing a small amount of Co and acidized after final annealing is considered to be because Co inhibited nitridation of the surface layer of the steel sheet during final annealing and also the nitrided layer formed during final annealing was removed as a result of acidizing.


<Experiment 2>

Next, in order to evaluate the influence of the acidizing conditions on the magnetic properties of non-oriented electrical steel sheets, acidizing was performed under various conditions and the high-frequency iron loss of each of the obtained non-oriented electrical steel sheets was measured.


Specifically, first, steel containing C: 0.0028%, Si: 3.4%, Mn: 0.6%, P: 0.01%, S: 0.0023%, Al: 1.0%, N: 0.0022%, Ti: 0.0011%, Nb: 0.0007%, O: 0.0020%, and Co: 0.0021% with the balance consisting of Fe and inevitable impurities was obtained by steelmaking in a vacuum furnace and cast into a steel ingot. The steel ingot was hot rolled to obtain a hot-rolled steel sheet with a sheet thickness of 1.8 mm, and the hot-rolled steel sheet was subjected to hot-rolled sheet annealing at 980° C. for 30 seconds to obtain a hot-rolled and annealed sheet. The hot-rolled and annealed sheet was pickled and then cold rolled to obtain a cold-rolled steel sheet with a final sheet thickness of 0.20 mm.


The obtained cold-rolled steel sheet was subjected to final annealing at 1050° C. for 10 seconds in an atmosphere of H2: N2=15:85 in vol %, and then subjected to acidizing. The acidizing was performed by immersing the steel sheet in hydrochloric acid for 10 seconds. Here, the concentration of the hydrochloric acid used was varied in the range of 1% to 50%.


Test pieces of 30 mm in width and 180 mm in length were cut out from the rolling direction (L direction) and transverse direction (C direction) of the non-oriented electrical steel sheet obtained in the foregoing manner, and the high-frequency iron loss (W10/400) of the test pieces was evaluated. Specifically, the iron loss W10/400 of the test pieces in the (L+C) direction at a maximum magnetic flux density of 1.0 T and a frequency of 400 Hz was measured by Epstein testing. Moreover, the concentration of N existing as AlN in the range from the surface of the non-oriented electrical steel sheet to a depth of 1/20 of the sheet thickness was measured by electrolytic extraction. FIGS. 3 and 4 illustrate the measurement results.


<Experiment 3>

Furthermore, non-oriented electrical steel sheets were produced in the same manner as in Experiment 2 except that the concentration of hydrochloric acid in acidizing was 20% and the acidizing time (immersion time) was varied in the range of 0.5 seconds to 100 seconds, and the high-frequency iron loss (W10/400) and the surface layer nitridation amount were measured. FIGS. 5 and 6 illustrate the measurement results.


As can be seen from the results illustrated in FIGS. 3 to 6, the high-frequency iron loss decreased significantly when the acid concentration was 3% to 30% and when the acidizing time was 1 second to 60 seconds. When the acid concentration was less than 3% or the acidizing time was less than 1 second, the iron loss remained high despite acidizing being performed. This is considered to be because, in the case where the acid concentration was low and in the case where the acidizing time was short, the effect of acidizing was insufficient and the nitrided layer formed during final annealing could not be removed sufficiently. When the acid concentration was more than 30% or the acidizing time was more than 60 seconds, too, the iron loss remained high. This is considered to be because the formation of an oxide film at the surface of the steel sheet progressed excessively during acidizing and as a result the removal of the nitrided layer was hindered.


The present disclosure is based on these discoveries. Embodiments of the present disclosure will be described in detail below, although the present disclosure is not limited to such embodiments.


[Chemical Composition]

The reasons for limiting the chemical composition of the non-oriented electrical steel sheet to the foregoing range in the present disclosure will be described.


C: 0.0050% or less


C is a harmful element that degrades iron loss by magnetic aging. In detail, if the C content is excessively high, C forms carbides that precipitate over time, causing an increase in iron loss. The C content is therefore limited to 0.0050% or less. The C content is preferably 0.0040% or less. Although no lower limit is placed on the C content, the C content is preferably 0.0001% or more from the viewpoint of reducing the decarburization costs in the refining process.


Si: 2.0% to 6.5%

Si is an element that has the effect of enhancing the specific resistance of steel and reducing iron loss. Si also has the effect of enhancing the strength of steel through solid solution strengthening. In order to achieve these effects, the Si content is 2.0% or more, and preferably 2.5% or more. If the Si content is more than 6.5%, slab cracking is likely to occur during production, resulting in decreased productivity. The Si content is therefore 6.5% or less, and preferably 6.0% or less.


Mn: 0.05% to 2.0%

Mn is an element that has the effect of enhancing the specific resistance of steel and reducing iron loss, as with Si. Mn also has the effect of forming sulfides and improving hot brittleness. In order to achieve these effects, the Mn content is 0.05% or more, and preferably 0.1% or more. If the Mn content is more than 2.0%, slab cracking is likely to occur during production, resulting in decreased productivity. The Mn content is therefore 2.0% or less, and preferably 1.5% or less.


P: 0.10% or less


If the P content is excessively high, cold rollability degrades. The P content is therefore 0.10% or less, and preferably 0.05% or less. No lower limit is placed on the P content, and the lower limit may be 0%. However, since P is an element that is highly effective in enhancing specific resistance and reducing eddy current loss, P may be optionally added within the foregoing range. From the viewpoint of reducing eddy current loss, the P content is preferably 0.001% or more and more preferably 0.003% or more.


S: 0.0050% or less


S forms sulfides as precipitates and inclusions and decreases productivity (hot rollability) and the magnetic properties of the non-oriented electrical steel sheet. The S content is therefore 0.0050% or less, and preferably 0.0030% or less. Since a lower S content is better, no lower limit is placed on the S content, and the lower limit may be 0%. Excessively reducing the S content, however, causes an increase in production costs, and accordingly the S content is preferably 0.0001% or more and more preferably 0.0005% or more.


Al: 0.3% to 3.0%

Al is an element that has the effect of enhancing the specific resistance of steel and reducing iron loss, as with Si. If the Al content is more than 3.0%, however, the steel becomes brittle and slab cracking is likely to occur during production. The Al content is therefore 3.0% or less, preferably 2.0% or less, and more preferably 1.5% or less. If the Al content is less than 0.3%, Al forms fine nitrides that precipitate, causing an increase in iron loss. The Al content is therefore 0.3% or more, and preferably 0.4% or more.


N: 0.0050% or less


N is a harmful element that forms nitrides and degrades magnetic properties. The N content is therefore 0.0050% or less, and preferably 0.0040% or less. Since a lower N content is better, no lower limit is placed on the N content, and the lower limit may be 0%. Excessively reducing the N content, however, causes an increase in production costs, and accordingly the N content is preferably 0.0005% or more and more preferably 0.0010% or more.


Co: 0.0005% to 0.0050%

Co is an element that has the effect of inhibiting nitridation of the surface layer of the steel sheet during final annealing, as mentioned above. The Co content is therefore 0.0005% or more, and preferably 0.001% or more. If the Co content is more than 0.0050%, the oxide film formed during final annealing increases in thickness, hindering the formation of an oxide layer by acidizing. The Co content is therefore 0.0050% or less, and preferably 0.0040% or less.


Ti: 0.0030% or less


Ti is a harmful element that forms fine carbonitrides that precipitate and increases iron loss. The adverse effect of Ti is particularly noticeable when the Ti content is more than 0.0030%. The Ti content is therefore 0.0030% or less, and preferably 0.0020% or less. Since a lower Ti content is better, no lower limit is placed on the Ti content, and the lower limit may be 0%. Excessively reducing the Ti content, however, causes an increase in production costs, and accordingly the Ti content is preferably 0.0001% or more and more preferably 0.0005% or more.


Nb: 0.0030% or less


Nb is a harmful element that forms fine carbonitrides that precipitate and increases iron loss. The adverse effect of Nb is particularly noticeable when the Nb content is more than 0.0030%. The Nb content is therefore 0.0030% or less, and preferably 0.0020% or less. Since a lower Nb content is better, no lower limit is placed on the Nb content, and the lower limit may be 0%. Excessively reducing the Nb content, however, causes an increase in production costs, and accordingly the Nb content is preferably 0.0001% or more and more preferably 0.0005% or more.


O: 0.0050% or less


O is a harmful element that forms oxides and degrades magnetic properties. The O content is therefore limited to 0.0050% or less. The O content is preferably 0.0040% or less. Since a lower O content is better, no lower limit is placed on the O content, and the lower limit may be 0%. Excessively reducing the O content, however, causes an increase in production costs, and accordingly the O content is preferably 0.0005% or more and more preferably 0.0010% or more.


A non-oriented electrical steel sheet in one embodiment of the present disclosure has a chemical composition containing the above-described components with the balance consisting of Fe and inevitable impurities.


(Group A)

The chemical composition may optionally further contain one or both of Sn and Sb in the following amounts.


Sn: 0.005% to 0.20%

Sn is an element that has the effect of improving recrystallized texture and improving magnetic flux density and iron loss. In the case of adding Sn, the Sn content is 0.005% or more in order to achieve the effect. If the Sn content is more than 0.20%, the effect is saturated. The Sn content is therefore 0.20% or less.


Sb: 0.005% to 0.20%

Sb is an element that has the effect of improving recrystallized texture and improving magnetic flux density and iron loss, as with Sn. In the case of adding Sb, the Sb content is 0.005% or more in order to achieve the effect. If the Sb content is more than 0.20%, the effect is saturated. The Sb content is therefore 0.20% or less.


(Group B)

The chemical composition may optionally further contain at least one selected from the group consisting of Ca, Mg, and REM (rare earth metal) in the following amount.


Ca, Mg, REM: 0.0005% to 0.020% in Total

Ca, Mg, and REM are components that have the effect of forming stable sulfides and improving grain growth. In the case of adding at least one selected from the group consisting of Ca, Mg, and REM, the total content of Ca, Mg, and REM is 0.0005% or more in order to achieve the effect. If the total content is more than 0.020%, the effect is saturated. The total content is therefore 0.020% or less.


(Group C)

The chemical composition may optionally further contain at least one selected from the group consisting of Cu, Cr, and Ni in the following amount.


Cu, Cr, Ni: 0.03% to 1.0% in total


Cu, Cr, and Ni are elements that have the effect of enhancing the specific resistance of steel and further reducing iron loss. In the case of adding at least one of Cu, Cr, and Ni, the total content of Cu, Cr, and Ni is 0.03% or more in order to achieve the effect. Since excessive addition decreases magnetic flux density, the total content is 1.0% or less.


(Group D)

The chemical composition may optionally further contain one or both of Ge and Ga in the following amount.


Ge, Ga: 0.0005% to 0.01% in total


Ge and Ga are elements that have the effect of improving texture. In the case of adding one or both of Ge and Ga, the total content of Ge and Ga is 0.0005% or more and preferably 0.0020% or more in order to achieve the effect. If the total content is more than 0.01%, the effect is saturated and the alloy cost increases. The total content is therefore 0.01% or less, and preferably 0.0050% or less.


(Group E)

The chemical composition may optionally further contain Zn in the following amount.


Zn: 0.001% to 0.05%

Zn is an element that has the effect of inhibiting nitridation during final annealing. In the case of adding Zn, the Zn content is 0.001% or more, and preferably 0.002% or more. If the Zn content is more than 0.05%, Zn forms sulfides, causing an increase in iron loss. The Zn content is therefore 0.05% or less, and preferably 0.01% or less.


(Group F)

The chemical composition may optionally further contain one or both of Mo and W in the following amount.


Mo, W: 0.001% to 0.05% in Total

Mo and W are elements that have the effect of improving high-temperature strength. Adding one or both of Mo and W can suppress surface defects (scab) in non-oriented electrical steel sheets. The steel sheet according to the present disclosure is high-alloy steel and its surface is easily-oxidizable, and thus the likelihood of scab caused by surface cracking is high. By adding one or both of Mo and W, such cracking can be suppressed. In the case of adding one or both of Mo and W, the total content of Mo and W is 0.001% or more and preferably 0.005% or more in order to sufficiently achieve the effect. If the total content is more than 0.05%, the effect is saturated and the alloy cost increases. The total content is therefore 0.05% or less, and preferably 0.020% or less.


[Nitrides]

Surface layer nitridation amount: 0.003% or less


As demonstrated in the foregoing experiments, there is a strong correlation between the surface layer nitridation amount and the high-frequency iron loss, and the iron loss decreases significantly when the surface layer nitridation amount is 0.003% or less. Hence, in the present disclosure, the surface layer nitridation amount at at least one surface (i.e. at least one side) of the non-oriented electrical steel sheet is 0.003% or less. Since a lower surface layer nitridation amount is more desirable from the viewpoint of reducing the high-frequency iron loss, no lower limit is placed on the surface layer nitridation amount, and the lower limit may be 0%. From the viewpoint of production, however, the surface layer nitridation amount may be 0.0001% or more, and may be 0.0005% or more. The “surface layer nitridation amount” herein refers to the amount of N existing as AlN in the range from the surface of the non-oriented electrical steel sheet to a depth of 1/20 of the sheet thickness. The surface layer nitridation amount can be measured by electrolytic extraction analysis. More specifically, the surface layer nitridation amount can be measured by the method described in the EXAMPLES section. It is preferable that the surface layer nitridation amount at both surfaces (sides) of the non-oriented electrical steel sheet satisfies the foregoing condition.


[Oxide Layer]

The non-oriented electrical steel sheet according to the present disclosure has, at at least one surface, an oxide layer containing one or both of Al and Si and having a thickness of 80 nm to 200 nm. The oxide layer is formed by acidizing after final annealing, as described later.


The oxide layer may contain Al oxide, Si oxide, or Al oxide and Si oxide. The oxide layer may optionally further contain other elements, for example, at least one selected from Fe, Co, and Mn. In the case where the oxide layer contains Fe, the Fe concentration in the oxide layer is not limited but is preferably less than 100 mass % relative to the total concentration of Al and Si.


Thickness of Oxide Layer: 80 nm to 200 nm

As a result of the steel sheet after final annealing being subjected to acidizing, the removal of the nitrided layer and the formation of the oxide layer progress and consequently the magnetic properties of the non-oriented electrical steel sheet are improved, as mentioned above. Here, the thickness of the oxide layer at the surface of the non-oriented electrical steel sheet finally obtained depends on the acidizing conditions. Our studies revealed that excellent magnetic properties are obtained when the thickness of the oxide layer is 80 nm or more. The thickness of the oxide layer is therefore 80 nm or more. If the oxide layer is excessively thick, the stacking factor of the steel sheet decreases. The thickness of the oxide layer is therefore 200 nm or less. The thickness of the oxide layer can be measured by scanning transmission electron microscope-energy dispersive X-ray spectroscopy (STEM-EDS). More specifically, the thickness of the oxide layer can be measured by the method described in the EXAMPLES section.


The concentration of Si contained in the oxide layer is not limited, and may be any concentration. If the Si concentration in the oxide layer is 12 at % (atomic %) or more, iron loss after stress relief annealing can be reduced. This is because, when the oxide layer contains 12 at % or more of Si, Al is preferentially oxidized during stress relief annealing to form a dense film and exhibits an excellent nitridation inhibiting effect. Hence, the Si concentration in the oxide layer is preferably 12 at % or more. Although no upper limit is placed on the Si concentration in the oxide layer, the Si concentration in the oxide layer is preferably 40 at % or less. The Si concentration in the oxide layer can be measured by STEM-EDS. More specifically, the Si concentration in the oxide layer can be measured by the method described in the EXAMPLES section.


The oxide layer may be amorphous, crystalline, or a composite oxide of amorphous and crystalline. The ratio of the crystalline phase to the total of the amorphous phase and the crystalline phase contained in the oxide layer is preferably in the range of 0% or more and 30% or less and more preferably in the range of 0% or more and 10% or less.


[Production Method]

Next, a method of producing a non-oriented electrical steel sheet in one embodiment of the present disclosure will be described.


In one embodiment of the present disclosure, a non-oriented electrical steel sheet can be produced by subjecting a steel material (slab) having the above-described chemical composition to the following treatments (1) to (3) sequentially:

    • (1) cold rolling
    • (2) final annealing
    • (3) acidizing.


In another embodiment of the present disclosure, hot rolling and hot-rolled sheet annealing may be performed before the cold rolling. In other words, in the other embodiment, a non-oriented electrical steel sheet can be produced by subjecting a steel material (slab) having the above-described chemical composition to the following treatments (1) to (5) sequentially:

    • (1) hot rolling
    • (2) hot-rolled sheet annealing
    • (3) cold rolling
    • (4) final annealing
    • (5) acidizing.


[Steel Material]

As the steel material, any steel material having the above-described chemical composition may be used. A typical example of the steel material is a steel slab.


The method of producing the steel material is not limited, and the steel material may be produced by any method. For example, steel is prepared by steelmaking in a refining process using a converter, an electric furnace, a vacuum degasser, etc., and then made into a steel material by a continuous casting method or an ingot casting and blooming method. A thin slab or thinner cast steel of 100 mm or less in thickness produced by a direct casting method may be used as the steel material.


[Hot Rolling]

In the case of performing hot rolling, the steel material is hot rolled to obtain a hot-rolled steel sheet. The hot rolling conditions are not limited, and hot rolling may be performed under commonly known conditions.


Typically, the steel material is reheated in a heating furnace or the like and then rolled. Alternatively, the cast steel material may be immediately hot rolled without reheating.


In the case of not performing hot rolling, the steel material can be directly subjected to cold rolling. In the case where hot rolling is omitted, it is preferable to use a thin slab or thinner cast steel as the steel material.


[Hot-Rolled Sheet Annealing]

In the case where hot rolling is performed, the obtained hot-rolled steel sheet is subjected to hot-rolled sheet annealing to obtain a hot-rolled and annealed sheet. The hot-rolled sheet annealing conditions are not limited. If the soaking temperature is less than 800° C., however, the effect of hot-rolled sheet annealing is small and the magnetic property improving effect may be insufficient. Accordingly, the soaking temperature in the hot-rolled sheet annealing is preferably 800° C. or more and more preferably 850° C. or more. If the soaking temperature is more than 1100° C., the production costs increase. In addition, due to coarsening of crystal grains, embrittlement fracture (breakage) tends to occur during subsequent cold rolling. The soaking temperature is therefore preferably 1100° C. or less and more preferably 1000° C. or less.


The soaking time in the hot-rolled sheet annealing is preferably 3 minutes or less and more preferably 1 minute or less, from the viewpoint of ensuring productivity. Although no lower limit is placed on the soaking time, the soaking time is preferably 1 second or more and more preferably 5 seconds or more.


[Cold Rolling]

Next, cold rolling is performed. In the case where hot rolling and hot-rolled sheet annealing are performed, the hot-rolled and annealed sheet is subjected to cold rolling to obtain a cold-rolled steel sheet having a final sheet thickness. In the case where hot rolling and hot-rolled sheet annealing are not performed, the steel material is directly subjected to cold rolling to obtain a cold-rolled steel sheet having a final sheet thickness. Cold rolling may be performed only once, or twice or more. In the case of performing cold rolling twice or more, intermediate annealing is performed between cold rolling. The cold rolling conditions are not limited, and cold rolling may be performed under commonly known conditions.


The final sheet thickness in the cold rolling, that is, the sheet thickness of the non-oriented electrical steel sheet finally obtained, is not limited and may be any thickness. If the non-oriented electrical steel sheet is excessively thick, however, iron loss increases. The final sheet thickness is therefore preferably 0.35 mm or less. Although no lower limit is placed on the sheet thickness, the sheet thickness is preferably 0.1 mm or more.


[Final Annealing]

The cold-rolled steel sheet obtained as a result of the cold rolling is subjected to final annealing. The final annealing conditions are not limited, and final annealing may be performed under commonly known conditions. From the viewpoint of coarsening the crystal grain size and further reducing iron loss, the soaking temperature in the final annealing is preferably 900° C. to 1200° C. and more preferably 1000° C. to 1100° C. For the same reason, the soaking time in the final annealing is preferably 1 second to 120 seconds and more preferably 5 seconds to 60 seconds.


[Acidizing]

After the final annealing, acidizing is performed on the surface of the steel sheet. The acidizing removes the nitrided layer formed during the final annealing. For the acidizing, it is necessary to use an acid containing at least one of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid at a total concentration of 3% or more. In particular, in order to set the Si concentration in the oxide layer to 12 at % or more, the total concentration of the acid is preferably 5% or more. If the concentration of the acid is excessively high, it is difficult to dispose of the acid after use. Accordingly, the total concentration of the acid is 30% or less and preferably 25% or less, from the viewpoint of ease of liquid waste disposal.


The acidizing time is 1 second to 60 seconds. In particular, in order to set the Si concentration in the oxide layer to 12 at % or more, the acidizing time is preferably 2 seconds or more. From the viewpoint of productivity, the acidizing time is preferably 20 seconds or less.


The acidizing method is not limited, and any method may be used. For example, the steel sheet may be immersed in the acid, or the acid may be sprayed onto the surface of the steel sheet.


The non-oriented electrical steel sheet can be produced by the method described above. After the acidizing, an insulating coating may be optionally formed on the surface of the non-oriented electrical steel sheet. The insulating coating may be formed under commonly known conditions.


EXAMPLES

In order to determine the effects according to the present disclosure, non-oriented electrical steel sheets were produced according to the following procedure and their magnetic properties were evaluated.


Steel slabs having the chemical compositions shown in Tables 1 to 3 were heated at 1120° C. for 30 minutes, and then hot rolled to obtain hot-rolled steel sheets of 1.9 mm in sheet thickness. The hot-rolled steel sheets were then subjected to hot-rolled sheet annealing at 950° C. for 30 seconds to obtain hot-rolled and annealed sheets. The hot-rolled and annealed sheets were pickled, and then cold rolled to obtain cold-rolled steel sheets having the final sheet thicknesses shown in Tables 4 to 6.


Subsequently, the cold-rolled steel sheets were subjected to finish annealing at 1020° C. for 20 seconds in an atmosphere of H2: N2=20:80 in vol %, and then subjected to acidizing under the conditions shown in Tables 4 to 6 to obtain non-oriented electrical steel sheets.


In Comparative Example No. 14 with an excessively high Mn content, slab cracking occurred during hot rolling and consequently production was discontinued. Likewise, in Comparative Example No. 15 with an excessively high Al content and Comparative Example No. 18 with an excessively high Si content, slab cracking occurred during hot rolling and consequently production was discontinued. In Comparative Example No. 21 with an excessively high P content, cracking occurred during cold rolling and consequently production was discontinued.


(Surface Layer Nitridation Amount)

Next, test pieces were collected from each of the obtained non-oriented electrical steel sheets, and electrolytic extraction analysis was conducted to measure the amount of N existing as AlN in the range from one surface of the non-oriented electrical steel sheet to a depth of 1/20 of the sheet thickness (surface layer nitridation amount).


(Thickness of Oxide Layer)

An oxide layer containing one or both of Al and Si was formed at the surface of the obtained non-oriented electrical steel sheet. The thickness of the oxide layer was measured by scanning transmission electron microscope-energy dispersive X-ray spectroscopy (STEM-EDS). Specifically, EDS map measurement was performed at intervals of 0.5 nm to obtain an elemental analysis map. In the elemental analysis map, a layer region with a O concentration of 15 at % or more at the surface of the steel sheet was taken to be an oxide layer and its thickness was determined.


(Si Concentration in Oxide Layer)

The Si concentration in the oxide layer was measured by STEM-EDS. Specifically, the average value of the Si concentration in the oxide layer was determined from the elemental analysis map obtained by the foregoing STEM-EDS measurement.


Moreover, a sample was collected from each of the obtained non-oriented electrical steel sheets, test pieces of 30 mm in width and 180 mm in length were cut out from the rolling direction (L direction) and the transverse direction (C direction), and the iron loss W10/400 in the (L+C) direction was measured by Epstein testing. In this example, the high-frequency iron loss was determined as good in the case where the measured iron loss W10/400 was less than the iron loss reference value (W/kg) given by the following formula (1):










iron


loss


reference


value



(

W
/
kg

)


=


21.8
×
t

+

7
.
5






(
1
)







where t is the sheet thickness (mm) of the non-oriented electrical steel sheet.


The measurement results are shown in Tables 4 to 6. As can be seen from these results, each non-oriented electrical steel sheet satisfying the conditions according to the present disclosure exhibited excellent reduction in iron loss in the high frequency range. According to the present disclosure, it is possible to reduce iron loss in the high frequency range without addition of a large amount of alloying elements, which causes a decrease in magnetic flux density. The non-oriented electrical steel sheet according to the present disclosure is thus suitable for use as a material for motor cores of hybrid electric vehicles, electric vehicles, high-speed generators, air conditioner compressors, vacuum cleaners, machine tools, etc.











TABLE 1









Chemical composition (mass %)*



















No.
C
Si
Mn
P
S
Al
Co
Ti
Nb
O
N
Others






















1
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


2
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


3
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


4
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


5
0.0025
3.5
0.4
0.01
0.0019
0.8

0.0002

0.0011
0.0009
0.0024
0.0027
Sn: 0.03


6
0.0025

1.9

0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



7
0.0025
3.8
0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



8
0.0025
3.8
0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



9
0.0025
3.8
0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



10
0.0025
3.8
0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



11
0.0025
3.8
0.5
0.01
0.0019
0.6
0.0029
0.0013
0.0011
0.0025
0.0024



12
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03


13
0.0028
3.2
0.8
0.01
0.0024
1.8
0.0024
0.0008
0.0012
0.0021
0.0020
Sn: 0.03


14
0.0029
3.5

2.5

0.01
0.0024
0.5
0.0021
0.0008
0.0011
0.0021
0.0028



15
0.0025
3.3
0.1
0.01
0.0024

3.5

0.0015
0.0008
0.0011
0.0021
0.0021



16
0.0019
4.2
0.3
0.01
0.0015
0.3
0.0026
0.0014
0.0012
0.0019
0.0027
Sb: 0.01


17
0.0019
5.6
0.3
0.01
0.0015
0.3
0.0027
0.0014
0.0012
0.0019
0.0027



18
0.0022

7.2

0.2
0.01
0.0024
0.3
0.0038
0.0008
0.0011
0.0021
0.0028



19
0.0021
4.0
0.4
0.01
0.0026
0.6
0.0032
0.0011
0.0013
0.0028
0.0024
Sn: 0.03


20
0.0021
4.0
0.4
0.01
0.0026
0.6
0.0032
0.0011
0.0013
0.0028
0.0024
Sn: 0.03


21
0.0026
3.2
0.1

0.25

0.0026
1.5
0.0025
0.0011
0.0013
0.0028
0.0024
Sn: 0.06


22
0.0024
3.4
1.2
0.01
0.0019
0.9
0.0024
0.0016
0.0014
0.0027
0.0021
Sn: 0.03


23
0.0024
3.3
1.8
0.01
0.0019
0.7
0.0024
0.0016
0.0014
0.0027
0.0021
Sn: 0.03


24
0.0018
3.5
0.2
0.01
0.0015
0.9
0.0021
0.0012
0.0009
0.0027
0.0021
Sb: 0.05


25
0.0017
3.6
0.5
0.01
0.0024
0.8
0.0027
0.0016
0.0014
0.0027
0.0021
Ca: 0.0034





*Balance consisting of Fe and inevitable impurities















TABLE 2









Chemical composition (mass %)*



















No.
C
Si
Mn
P
S
Al
Co
Ti
Nb
O
N
Others






















26
0.0017
3.6
0.5
0.01
0.0026
0.8
0.0027
0.0016
0.0014
0.0027
0.0021
Mg: 0.0025


27
0.0017
3.6
0.5
0.01
0.0027
0.8
0.0027
0.0016
0.0014
0.0027
0.0021
REM: 0.0072


28
0.0025
3.3
0.6
0.01

0.0059

0.9
0.0019
0.0018
0.0013
0.0029
0.0026
Sn: 0.04


29
0.0025
3.8
0.2
0.01
0.0015
0.5
0.0021

0.0041

0.0013
0.0029
0.0026
Sn: 0.04


30
0.0025
3.8
0.2
0.01
0.0015
0.5
0.0021
0.0007

0.0038

0.0029
0.0026
Sn: 0.04


31
0.0025
3.8
0.2
0.01
0.0015
0.5
0.0021
0.0007
0.0011

0.0064

0.0026
Sn: 0.04


32
0.0025
3.8
0.2
0.01
0.0015
0.5
0.0021
0.0007
0.0011
0.0021

0.0065

Sn: 0.04


33
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03


34
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03


35
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03


36
0.0026
3.4
0.9
0.01
0.0026
1.4
0.0019
0.0018
0.0012
0.0021
0.0023
Sn: 0.03


37
0.0026
3.4
0.9
0.01
0.0026
1.4
0.0019
0.0018
0.0012
0.0021
0.0023
Sn: 0.03


38
0.0026
3.4
0.9
0.01
0.0026
1.4
0.0019
0.0018
0.0012
0.0021
0.0023
Sn: 0.03


39
0.0025
3.7
0.8
0.01
0.0021
0.8
0.0021
0.0013
0.0013
0.0032
0.0031
Sn: 0.03, Ca: 0.0029


40
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


41
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


42
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


43
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


44
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


45
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


46
0.0025
2.3
0.1
0.01
0.0024
2.8
0.0015
0.0008
0.0011
0.0021
0.0021



47
0.0025
3.5
0.4
0.006
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


48
0.0025
3.5
0.4
0.05
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03


49
0.0025
3.5
0.4
0.09
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03





*Balance consisting of Fe and inevitable impurities















TABLE 3









Chemical composition (mass %)*



















No.
C
Si
Mn
P
S
Al
Co
Ti
Nb
C
N
Others






















50
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cu: 0.30


51
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cu: 0.50


52
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cr: 0.10


53
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cr: 0.30


54
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cr: 0.90


55
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Ni: 0.04


56
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Ni: 0.50


57
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Ni: 0.80


58
0.0025
3.5
0.4
0.01
0.0019
0.8
0.0021
0.0011
0.0009
0.0024
0.0027
Sn: 0.03, Cu: 0.30, Cr: 0.10, Ni: 0.10


59
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Zn: 0.0015


60
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Zn: 0.0045


61
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Zn: 0.021


62
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Mo: 0.0029


63
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Mo: 0.0300


64
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, Zn: 0.0068, Mo: 0.0050


65
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, W: 0.0011


66
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, W: 0.014


67
0.0021
4.1
0.5
0.01
0.0023
0.7
0.0024
0.0012
0.0013
0.0023
0.0022
Sn: 0.03, W: 0.036


68
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ga: 0.0012


69
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ge: 0.0024


70
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ga: 0.0034, Ge: 0.0042


71
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ga: 0.0067


72
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ge: 0.081


73
0.0028
3.2
0.8
0.01
0.0024
1.2
0.0024
0.0008
0.0012
0.0021
0.0019
Sn: 0.03, Ga: 0.0008, Ge: 0.0007





*Balance consisting of Fe and inevitable impurities
















TABLE 4









Measurement results














Final
Acidizing
Surface
Oxide layer



















sheet

Acid
Acid-
layer

Si
Iron loss





thick-

concen-
izing
nitridation
Thick-
concen-
reference



ness

tration
time
amount
ness
tration
value
W10/400


No.
(mm)
Acid
(wt %)
(sec)
(mass %)
(nm)
(at %)
(W/kg)
(W/kg)
Remarks




















1
0.25
Phosphoric acid
10
5
0.0019
 80
35
13.0
11.3
Example


2
0.25
Hydrochloric acid
10
5
0.0018
 90
35
13.0
11.2
Example


3
0.25
Sulfuric acid
10
5
0.0015
 85
35
13.0
11.1
Example


4
0.25
Nitric acid
10
5
0.0014
 90
35
13.0
11.0
Example


5
0.25
Phosphoric acid
10
5

0.0054

 80
3
13.0
13.8
Comparative Example


6
0.25
Phosphoric acid
10
5
0.002 
 90
4
13.0
14.2
Comparative Example


7
0.30
Nitric acid + hydrochloric acid
20
3
0.0015
 85
38
14.0
10.9
Example


8
0.30
Hydrochloric acid + phosphoric acid
15
15 
0.0021
120
26
14.0
11.2
Example


9
0.30
Hydrochloric acid
2
10 

0.0058

30
1
14.0
14.9
Comparative Example


10
0.30
Hydrochloric acid
 8

80


0.0049


250

3
14.0
14.1
Comparative Example


11
0.30
Nitric acid + hydrochloric
15
5
0.0015
 90
26
14.0
12.1
Example




acid + phosphoric acid


12
0.27
Sulfuric acid + hydrochloric
25
25 
0.0018
150
39
13.4
11.7
Example




acid + phosphoric acid


13
0.25
Nitric acid
20
5
0.0016
 90
29
13.0
11.2
Example


14









Comparative Example


15









Comparative Example


16
0.25
Phosphoric acid
25
5
0.0019
105
32
13.0
10.8
Example


17
0.25
Phosphoric acid
25
5
0.0018
100
32
13.0
9.9
Example


18









Comparative Example


19
0.35
Nitric acid
15
10 
0.0016
115
23
15.1
12.5
Example


20
0.20
Nitric acid
15
20 
0.0015
125
23
11.9
9.1
Example


21









Comparative Example


22
0.25
Hydrochloric acid
 5
30 
0.0021
105
10
13.0
11.8
Example


23
0.25
Hydrochloric acid
 5
30 
0.0020
105
10
13.0
11.5
Example


24
0.27
Phosphoric acid
 3
50 
0.0025
150
8
13.4
11.9
Example


25
0.25
Nitric acid + hydrochloric acid
 8
20 
0.0021
100
12
13.0
11.0
Example



















TABLE 5









Measurement results














Final
Acidizing
Surface
Oxide layer



















sheet

Acid

layer

Si
Iron loss





thick-

concen-
Acidizing
nitridation
Thick-
concen-
reference



ness

tration
time
amount
ness
tration
value
W10/400


No.
(mm)
Acid
(wt %)
(sec)
(mass %)
(nm)
(at %)
(W/kg)
(W/kg)
Remarks




















26
0.25
Sulfuric acid
10
15
0.0015
95
27
13.0
10.9
Example


27
0.25
Sulfuric acid
10
15
0.0015
95
27
13.0
10.9
Example


28
0.25
Hydrochloric acid + phosphoric acid
20
5
0.0024
80
15
13.0
14.4
Comparative Example


29
0.25
Hydrochloric acid + phosphoric acid
20
5
0.0021
80
15
13.0
15.2
Comparative Example


30
0.25
Hydrochloric acid + phosphoric acid
20
5
0.0022
80
15
13.0
15.1
Comparative Example


31
0.25
Hydrochloric acid + phosphoric acid
20
5
0.0021
80
15
13.0
14.8
Comparative Example


32
0.25
Hydrochloric acid + phosphoric acid
20
5

0.0054

80
15
13.0
16.5
Comparative Example


33
0.20
Hydrochloric acid + nitric acid
15
4
0.0019
85
28
11.9
9.2
Example


34
0.25
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
13.0
10.4
Example


35
0.30
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
14.0
11.8
Example


36
0.15
Sulfuric acid + phosphoric acid
25
2
0.0013
90
33
10.8
8.7
Example


37
0.20
Sulfuric acid + phosphoric acid
25
2
0.0012
90
33
11.9
9.4
Example


38
0.25
Sulfuric acid + phosphoric acid
25
2
0.0012
90
33
13.0
10.6
Example


39
0.25
Sulfuric acid + phosphoric acid
25
2
0.0012
90
33
13.0
10.8
Example


40
0.25
Nitric acid
3
1
0.0024
85
6
13.0
11.9
Example


41
0.25
Nitric acid
3
60
0.0022
125 
8
13.0
11.8
Example


42
0.25
Nitric acid
30
1
0.0021
90
34
13.0
11.7
Example


43
0.25
Nitric acid
30
60
0.0021
130 
35
13.0
11.7
Example


44
0.25
Phosphoric acid
3
8

0.0054


75

5
13.0
14.1
Comparative Example


45
0.25
Phosphoric acid
3
5

0.0056


50

3
13.0
14.3
Comparative Example


46
0.25
Nitric acid
20
5
0.0008
100 
39
13.0
11.0
Example


47
0.25
Hydrochloric acid
10
5
0.0018
90
35
13.0
11.4
Example


48
0.25
Hydrochloric acid
10
5
0.0018
90
35
13.0
11.2
Example


49
0.25
Hydrochloric acid
10
5
0.0018
90
35
13.0
11.1
Example



















TABLE 6









Measurement results














Final
Acidizing
Surface
Oxide layer



















sheet

Acid
Acid-
layer

Si
Iron loss





thick-

concen-
izing
nitridation
Thick-
concen-
reference



ness

tration
time
amount
ness
tration
value
W10/400


No.
(mm)
Acid
(wt %)
(sec)
(mass %)
(nm)
(at %)
(W/kg)
(W/kg)
Remarks




















50
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
11.0
Example


51
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.9
Example


52
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
11.0
Example


53
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.9
Example


54
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.8
Example


55
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.9
Example


56
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.9
Example


57
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.8
Example


58
0.25
Sulfuric acid
10
5
0.0015
85
25
13.0
10.8
Example


59
0.30
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
14.0
10.8
Example


60
0.30
Hydrochloric acid + nitric acid
15
4
0.0017
85
28
14.0
11.7
Example


61
0.30
Hydrochloric acid + nitric acid
15
4
0.0016
85
28
14.0
11.6
Example


62
0.30
Hydrochloric acid + nitric acid
15
4
0.0015
85
28
14.0
11.5
Example


63
0.30
Hydrochloric acid + nitric acid
15
4
0.0015
85
28
14.0
11.5
Example


64
0.30
Hydrochloric acid + nitric acid
15
4
0.0015
85
28
14.0
11.5
Example


65
0.30
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
14.0
11.7
Example


66
0.30
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
14.0
11.7
Example


67
0.30
Hydrochloric acid + nitric acid
15
4
0.0018
85
28
14.0
11.7
Example


68
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.6
Example


69
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.6
Example


70
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.5
Example


71
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.5
Example


72
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.5
Example


73
0.27
Sulfuric acid + hydrochloric acid + phosphoric acid
25
25
0.0018
150
35
13.4
11.6
Example








Claims
  • 1. A non-oriented electrical steel sheet comprising a chemical composition containing, in mass %,C: 0.0050% or less,Si: 2.0% to 6.5%,Mn: 0.05% to 2.0%,P: 0.10% or less,S: 0.0050% or less,Al: 0.3% to 3.0%,N: 0.0050% or less,Co: 0.0005% to 0.0050%,Ti: 0.0030% or less,Nb: 0.0030% or less, andO: 0.0050% or less,with a balance consisting of Fe and inevitable impurities,wherein at at least one surface of the non-oriented electrical steel sheet, an amount of N existing as AlN in a range from the surface to a depth of 1/20 of a thickness of the non-oriented electrical steel sheet is 0.003 mass % or less, andthe surface has an oxide layer containing one or both of Al and Si and having a thickness of 80 nm to 200 nm.
  • 2. The non-oriented electrical steel sheet according to claim 1, wherein a Si concentration in the oxide layer is 12 at % or more.
  • 3. The non-oriented electrical steel sheet according to claim 1, wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F: group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,group E: Zn: 0.001% to 0.05%, andgroup F: one or both of Mo and W: 0.001% to 0.05% in total.
  • 4. A method of producing a non-oriented electrical steel sheet, the method comprising: subjecting a steel material to cold rolling once or twice or more with intermediate annealing therebetween to obtain a cold-rolled steel sheet, the steel material having a chemical composition containing, in mass %, C: 0.0050% or less, Si: 2.0% to 6.5%, Mn: 0.05% to 2.0%, P: 0.10% or less, S: 0.0050% or less, Al: 0.3% to 3.0%, N: 0.0050% or less, Co: 0.0005% to 0.0050%, Ti: 0.0030% or less, Nb: 0.0030% or less, and O: 0.0050% or less, with a balance consisting of Fe and inevitable impurities;subjecting the cold-rolled steel sheet to final annealing to produce a non-oriented electrical steel sheet; andsubjecting, after the final annealing, a surface of the steel sheet to acidizing for 1 second to 60 seconds using an acid containing at least one selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid at a total concentration of 3 wt % to 30 wt %.
  • 5. The method of producing a non-oriented electrical steel sheet according to claim 4, comprising: subjecting, before the cold rolling, the steel material to hot rolling to obtain a hot-rolled steel sheet; andsubjecting the hot-rolled steel sheet to hot-rolled sheet annealing to obtain a hot-rolled and annealed sheet,wherein the hot-rolled and annealed sheet is subjected to the cold rolling.
  • 6. The method of producing a non-oriented electrical steel sheet according to claim 4, wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F: group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,group E: Zn: 0.001% to 0.05%, andgroup F: one or both of Mo and W: 0.001% to 0.05% in total.
  • 7. The non-oriented electrical steel sheet according to claim 2, wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F: group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,group E: Zn: 0.001% to 0.05%, andgroup F: one or both of Mo and W: 0.001% to 0.05% in total.
  • 8. The method of producing a non-oriented electrical steel sheet according to claim 5, wherein the chemical composition further contains, in mass %, one or more groups out of the following groups A to F: group A: one or both of Sn: 0.005% to 0.20% and Sb: 0.005% to 0.20%,group B: at least one selected from the group consisting of Ca, Mg, and REM: 0.0005% to 0.020% in total,group C: at least one selected from the group consisting of Cu, Cr, and Ni: 0.03% to 1.0% in total,group D: one or both of Ge and Ga: 0.0005% to 0.01% in total,group E: Zn: 0.001% to 0.05%, andgroup F: one or both of Mo and W: 0.001% to 0.05% in total.
Priority Claims (1)
Number Date Country Kind
2022-015254 Feb 2022 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2023/001792 1/20/2023 WO