JP5724727B2 - Method for producing Fe-based metal plate having high degree of {200} plane integration - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is suitable for applications such as electric motors, generators, transformer cores, and the like, and a method for producing an Fe-based metal plate having a high {200} plane integration degree that can contribute to downsizing and energy loss reduction of these magnetic cores. About.

  Conventionally, magnetic steel sheets made of an alloy of silicon or the like have been used for magnetic cores of electric motors, generators, transformers and the like. Among electrical steel sheets, non-oriented electrical steel sheets with relatively random crystal orientations can be manufactured at low cost, and are therefore generally used in motors and transformers for home appliances. Since the crystal orientation of this non-oriented electrical steel sheet is random, a high magnetic flux density cannot be obtained. On the other hand, grain-oriented electrical steel sheets with the same crystal orientation are applied to high-end applications such as drive motors for HV vehicles because high magnetic flux density is obtained. However, the production of grain-oriented electrical steel sheets that are currently industrialized requires a long heat treatment and is expensive.

  As a technique to increase the degree of integration of a specific crystal orientation by applying a magnetic field during recrystallization or after recrystallization in methods other than the manufacturing method of industrialized grain-oriented electrical steel sheets, particularly in the temperature raising process of finish annealing, There is a technology like this.

In Patent Document 1, in the method for producing a non-oriented electrical steel sheet, a magnetic field is applied to the initial stage of recovery or recrystallization at the time of cold rolling finish annealing of a silicon steel sheet containing Si: 2 to 4 mass%. A technique for improving the magnetic characteristics by randomization is disclosed. In this technique, the application direction of the magnetic field is the same as the rolling direction of the steel plate, and the integration degree of {hk0} to {100} <001> is increased, and the integration degree of the {111} plane orientation is reduced, thereby It is intended to be magnetized in all directions in the plane.
Patent Document 2 discloses a technique aimed at applying a magnetic field in the rolling direction during recrystallization and promoting crystal orientation in the rolling direction to <001> in the method for producing a unidirectional electrical steel sheet. ing.

In Patent Document 3, in a method of manufacturing a bi-directional electrical steel sheet, a steel sheet to be treated is heat-treated while applying a static magnetic field or an alternating magnetic field in a direction of easy magnetization in a temperature range of 250 ° C. or lower in a Curie temperature or lower, so Techniques aimed at reducing the above are disclosed.
In Non-Patent Document 1, as a result of hot forging armco iron and recrystallizing a cold-rolled plate at 700 ° C. while applying a maximum magnetic field of 1.5 T, the result is parallel to the magnetic field application direction. It has been reported that texture with <100> orientation increases.

  However, satisfactory magnetic properties cannot be obtained simply by applying a magnetic field in the easy magnetization direction of a steel plate that has already been recrystallized as in Patent Document 3. In addition, even when recrystallization is performed while applying a magnetic field in the rolling direction or the easy magnetization direction of a steel sheet as in Patent Documents 1 and 2 and Non-Patent Document 1, it is not possible to obtain satisfactory magnetic properties by itself.

JP-A-5-33062 Japanese Patent Laid-Open No. 10-158741 JP 2009-127073 A

Scandinavian Journal of Metallurgy 10 (1981) P.3-8

In order to realize an electromagnetic steel sheet with high magnetic flux density and low iron loss, it is necessary to perform heat treatment for a long time for decarburization and annealing or cold rolling at a high pressure ratio, which is a cause of high cost.
Therefore, the object of the present invention is to use an Fe-based metal plate having a high {200} texture and further imparted with a high electrical resistance by using a heat treatment for a short time or a cold-rolled plate having a normal reduction rate. It is providing the method of manufacturing efficiently and stably.

  The present inventors examined a method for further increasing the {200} plane integration degree of the α-Fe phase based on the method for increasing the {100} plane integration degree by heat treatment in a magnetic field as disclosed in the above-mentioned prior art. did. As a result, there is a limit to the improvement of the degree of integration only by the application of a magnetic field, and in order to further increase the texture of the whole plate with an increased degree of integration of {100} planes formed by recovery / recrystallization in the magnetic field, We found that it was necessary to combine with other means.

Then further studies as a result, the steel plate with increased {100} plane of the integration by the heat treatment in a magnetic field and heated to a temperature of more than _three points A, different metals other than Fe from the surface was alloyed by diffusion into the iron plate, It discovered that the {200} plane integration degree of an iron plate became high when it cooled after that.
The gist of the present invention as a result of such examination is as follows.

(1) A method for producing an Fe-based metal plate having a high degree of {200} plane integration,
(A 1 ) a step of preparing a base metal plate made of an α-γ transformation component Fe-based metal and having a processed structure ;
(A2) attaching a ferrite-forming element to one side or both sides of the prepared base metal plate;
(B) the attached base metal plate ferrite forming element, and heated to ₃ A base material while applying a magnetic field at the Curie temperature or less, the diffusion of ferrite forming elements in a part or all of the base metal plate And alloying step,
(C) The base metal plate is heated and held at a temperature of A ₃ or higher and 1300 ° C. or lower to increase the {200} plane integration degree of the α-Fe phase alloyed by the diffusion of the ferrite-forming elements { 222} reducing the degree of surface integration;
(D) the base metal plate is cooled to a temperature of A less than ₃ points, when the gamma-Fe phase in the region not alloyed is transformed to alpha-Fe phase, the region {200} plane integration of 30 % Of the Fe-based metal having a high {200} plane integration characterized by having a step of adjusting the {222} plane integration degree to 0.01% or more and 30% or less. A manufacturing method of a board.

(2) In the method for producing an Fe-based metal plate according to (1), instead of the steps (a2) and (b) , a magnetic field is applied to the prepared base metal plate (e) While performing a heat treatment to heat the Fe-based metal to a Curie temperature (° C.) ± 50 ° C.,
(F) attaching a ferrite-forming element to one or both surfaces of the base metal plate after the heat treatment;
The deposited metal plate (g) ferrite forming element and heated to ₃ A base material, some or all of the base metal plate to diffuse the ferrite forming elements, as engineering for alloying
Method of manufacturing a Fe-based metal plate having a high {200} plane integration characterized by having and.

(3) A high {200} plane integration degree according to (1) or (2), wherein a magnetic field having a magnetic flux density of 0.01 T or more is applied to the base metal plate perpendicularly to the rolling direction. The manufacturing method of the Fe-type metal plate which has this.
(4) A magnetic field having a magnetic flux density of 0.01 T or more is applied to the base metal plate perpendicular to the rolling direction, and a magnetic flux density of 0.2 T or more is applied in parallel to the rolling direction. The manufacturing method of the Fe-type metal plate which has the high {200} plane integration degree as described in said (1) or (2).

According to the present invention, an Fe-based metal plate in which {200} planes of α-Fe are highly integrated in a rolling surface or both in a rolling surface and a surface perpendicular thereto is heat-treated for a long time as in the prior art. Can be produced without the need for Further, since the obtained Fe-based metal plate has the <100> axis accumulated in the rolling plane or a plane perpendicular thereto, a higher magnetic flux density can be obtained when the same magnetic field is applied.
Furthermore, since an Fe-based metal plate having a diffusion layer of a dissimilar metal that increases the electrical resistance at least in the surface layer portion is obtained, a great effect is expected in reducing high-frequency iron loss.

It is a figure explaining the process for obtaining the Fe-type metal plate which raised {200} plane integration degree. It is a figure explaining the form of the Fe-type metal plate which raised {200} plane integration degree.

  In the present invention, as a method for producing an Fe-based metal plate having a high {200} plane integration degree, a {100} texture is formed at least on the surface layer portion of the metal plate, and a part or all of this region from the surface. Then, the ferrite-forming elements are diffused by heating to further increase the degree of {200} texture accumulation of the entire Fe-based metal plate during cooling.

Such invention, the present inventors have, {100} crystal grains in the formed texture on the surface, the grain growth preferentially in more than _three points A heating process for the diffusion of the ferrite forming elements Furthermore, it is based on the fact that the {200} plane integration degree of the plate surface of the Fe-based metal plate is increased when the ferrite-forming element is formed into a diffusion alloy and then cooled. .

Description of the Basic Principle of the Present Invention First, the basic principle of the present invention that provides a high {200} plane integration degree will be described with reference to FIG.

(A) Preparation of base metal plate A base metal plate made of an α-γ transformation component Fe-based metal and having a rolled microstructure is prepared, and a ferrite-forming element is formed on one or both sides of the metal plate. Is deposited by vapor deposition. (See the state in Fig. 1-a)
Hereinafter, a case where a pure iron plate is used as a base metal plate and Al is used as a ferrite forming element will be described as an example.
(B) Texture seeding and bud formation A base metal pure iron plate with Al adhering as a ferrite-forming element is recrystallized by heating to A ₃ point of the base material, and a part or the whole of the pure iron plate is made of Al. Is diffused and alloyed with the base material. At that time, heating is performed while applying a magnetic field perpendicular to the rolling direction at a temperature equal to or lower than the Curie temperature.
By applying a magnetic field at the recovery stage of heating or at the initial stage of recrystallization, the {100} texture is perpendicular to the magnetic field application direction (parallel to the rolling direction) in the entire surface layer or thickness direction of the pure iron plate. Is formed. (Refer to the state of Fig. 1-b1)
Further, in the region where Al is diffused and alloyed, an α single-phase component is formed, and in that region, the γ phase is transformed to the α phase. At that time, since the transformation takes place with the orientation of the {100} texture formed in the process of recovery recrystallization, a {100} oriented structure is formed even in the alloyed region.

Saving (c) texture, high integration pure iron further heated to a temperature of 1300 ° C. or less than _three points A, hold.
Since the region of the α single phase component is an α-Fe phase that does not undergo γ transformation, {100} grains are preserved as they are, and {100} grains preferentially grow in the region, and the {200} plane integration degree Will increase. Further, the region that is not the α single phase component is transformed from the α phase to the γ phase.
When the holding time is lengthened, {100} grains grow preferentially due to grain engagement. As a result, the {200} plane integration degree further increases. In addition, with the diffusion of Al, the region transformed into an Fe—Al alloy transforms from the γ phase to the α phase. At that time, α grains already oriented in {100} are formed in the region adjacent to the region to be transformed, and when transforming from the γ phase to the α phase, the transformation takes place in the form of taking over the crystal orientation of the adjacent α grains. As a result, the holding time becomes longer and the {200} plane integration degree further increases. (See the state in Fig. 1-c)

(D) the growth of pure iron texture cooled to a temperature of A less than ₃ points. At this time, the γ-Fe phase in the non-alloyed inner region is transformed into the α-Fe phase. This internal region is adjacent to the region which is oriented α grains and already {100} in a temperature range of more than _three points A, when transformed into α phase from γ phase, of the adjacent α grains It takes over the crystal orientation and transforms. For this reason, the {200} plane integration degree also increases in that region.
By this phenomenon, a high {200} plane integration degree can be obtained even in a non-alloyed region.
In the previous stage (c), when the A3 is held at ₃ points or more until the entire plate is alloyed, a structure with a high {200} plane integration degree is already formed over the entire plate. Cooling while maintaining the initial state.

In this example, the ferrite forming element was first attached to the base material and then the heat treatment was performed. First, (e) the Curie temperature of iron ± 50 ° C. while applying a magnetic field to the pure iron plate of the base material. performing heat treatment step of heating up to temperature and then, (f) on one side or both sides of the net iron plate after heat treatment after attaching the Al, (g) a pure iron plate adhering of Al, a ₃ of the base material Tenma May be heated to cause Al to diffuse into a part or the whole of the pure iron plate to be alloyed with the base material, and then the steps (c) and (d) may be performed.

Moreover, although the magnetic field was applied in the direction perpendicular to the rolling direction of the base metal sheet, it may be applied in a direction parallel to the rolling direction in addition to the perpendicular direction (see the state of FIG. 1-b2).
By applying a magnetic field in a direction parallel to the rolling direction, the ferrite-forming element is diffused, and after cooling, a {100} texture can be formed also in the plane direction perpendicular to the rolling direction. {100} textures can be formed in two directions, a parallel direction and a vertical direction.

  Although the basic principle of the present invention has been described above, the reasons for limiting the individual conditions that define the production method of the present invention and the preferable conditions for carrying out the present invention will be further described. In the following description,% of the element content means mass%.

Fe-based metal plate as a base material (basic requirements for Fe-based metals)
In the present invention, first, {100} -oriented crystal grains that form buds for increasing the degree of {200} plane integration are formed in a surface layer portion or a plate of a base metal plate made of Fe-based metal having a processed structure. Then, finally, the γ-α transformation is advanced in the plate in such a way as to inherit the crystal orientation of the α grains serving as the buds, thereby increasing the {200} plane integration degree of the entire plate.
For this reason, the Fe-based metal used for the base metal plate needs to have a processed structure and an α-γ transformation component system composition. If the Fe-based metal used for the base metal plate has a processed structure, it can form {100} -oriented textured buds by the action of a magnetic field when recovered and recrystallized by heating, In addition, in the case of an α-γ transformation component, an α single-phase component region can be formed by forming a ferrite-forming element into a diffusion alloy in the plate.
Note that the α-γ transformation system has, for example, A ₃ points in a range of about 600 ° C. to 1000 ° C., and if it is less than A ₃ points, the α phase becomes a main phase exceeding 50% by volume, and A ₃ points. The above is a component system in which the γ phase is the main phase.

(Composition of base metal plate)
In principle, the present invention is applicable to an Fe-based metal having an α-γ transformation component, and is not limited to an Fe-based metal having a specific composition range.
Typical components of the α-γ transformation system include pure iron (including industrially produced relatively high-purity iron having a purity of 99.9% or more), ordinary steel, and the like. This steel is exemplified.
For example, pure iron or steel consisting of C: 1 ppm to 0.2%, the balance Fe and unavoidable impurities is used as a base, and additional elements are appropriately contained.
In addition, silicon steel of α-γ transformation system component having C: 0.1% or less and Si: 0.1-2.5% as basic components may be used.
Other impurities include trace amounts of Mn, Ni, Cr, Al, Mo, W, V, Ti, Nb, B, Cu, Co, Zr, Y, Hf, La, Ce, N, O, P, S and the like are included.

(Formation of processed structure)
What is necessary is just to form the process structure of a base metal plate in accordance with a conventional method, such as rolling. For example, a material metal plate hot-rolled from a slab made of Fe-based metal having a composition of α-γ transformation component system, or a material metal plate cold-rolled after hot rolling, and the metal plate Finally, cold rolling may be performed to leave the processed structure. In that case, the cold rolling rate is preferably 40% or more. If the cold rolling rate is less than that value, the textured buds oriented in {200} cannot be sufficiently formed.

(Thickness of base metal plate)
The thickness of the base metal plate is 10 μm or more and 5 mm or less. When the thickness is less than 10 μm, the number of stacked layers increases when the layers are used as a magnetic core, resulting in an increase in gaps and a high magnetic flux density cannot be obtained. If the thickness exceeds 5 mm, the {100} texture cannot be sufficiently grown after cooling after the diffusion treatment, and a high magnetic flux density cannot be obtained.

Dissimilar metals (types of dissimilar metals)
Dissimilar metals other than Fe are diffused in the base metal plate to increase the {100} region in the thickness direction of the steel plate. A ferrite-forming element is selected as the dissimilar metal used.
For this purpose, a heterogeneous metal is deposited as a second layer on one or both sides of a base metal plate made of an Fe-based metal as an α-γ transformation component, and the region in which the element diffuses and forms an alloy is formed in an α single phase. As a system component, in addition to the region transformed into the α phase, it can be stored as {100} oriented buds for increasing the {200} plane integration degree in the plate.
As such a ferrite forming element, at least one of Al, Cr, Ga, Ge, Mo, Sb, Si, Sn, Ti, V, W, and Zn can be used alone or in combination.

(Different metal adhesion method)
Various methods such as plating methods such as hot dipping and electrolytic plating, rolling clad methods, dry processes such as PVD and CVD, and powder coating are used as the method for adhering different types of metal to the surface of the base metal plate in layers. can do. A plating method or a rolling clad method is suitable as a method for depositing dissimilar metals efficiently for industrial implementation.
The adhesion thickness of the dissimilar metal before heating is desirably 0.05 μm or more and 1000 μm or less. If the thickness is less than 0.05 μm, a sufficient {200} plane integration degree cannot be obtained. Further, if it exceeds 1000 μm, the thickness becomes thicker than necessary even when the dissimilar metal remains on the surface.

Magnetic field application and heat treatment conditions (magnetic field application time)
In the present invention, as described above, an Fe-based metal plate having a processed structure after cold rolling is heat-treated, and a magnetic field is applied at the stage of recovery of the heating process or at the initial stage of recrystallization. A {100} texture is formed in a direction perpendicular to the magnetic field application direction in the entire surface layer portion or thickness direction of the plate, and simultaneously with the formation of the {100} texture or after the {100} texture is formed Then, the dissimilar metal is diffused into a part or all of the region where the {100} texture is formed from the surface, and the entire Fe-based metal plate is converted to {100} during cooling.
Therefore, the step of applying a magnetic field and performing the heat treatment may be performed independently before attaching the dissimilar metal to the Fe-based metal plate, or the metal plate to which the dissimilar metal is first attached is heated to diffuse the dissimilar metal. You may carry out in the temperature rising process at the time of making. Either way, the same effect can be obtained.

(Heating conditions when applying a magnetic field)
The temperature range for applying the magnetic field may be up to the Curie temperature (770 ° C for pure iron) because the effect of crystal orientation cannot be obtained because the Fe-based metal plate is not magnetized at a temperature higher than the Curie temperature. Even if a magnetic field is applied, there is no particular problem. Moreover, since recovery and recrystallization hardly occur at 200 ° C. or less and there is no effect of applying a magnetic field, it is preferable to apply a magnetic field at 200 ° C. or more. When it is carried out independently prior to the diffusion of the different metal, it is preferably carried out in a temperature range of 200 ° C. to (base material Curie temperature ± 50) ° C.
The heating rate during heating is preferably 0.1 ° C./sec or more and 500 ° C./sec or less. {200} plane oriented buds are efficiently formed at a temperature rising rate within this range.

(Magnetic field application method and strength)
The magnetic field is applied to the cold-rolled Fe-based metal plate in a direction (plate thickness direction) perpendicular to the cold rolling direction in a temperature range equal to or lower than the Curie temperature. Alternatively, in addition to the vertical direction, it is further applied in a direction parallel to the rolling direction (long plate direction).
By the action of this magnetic field, when the cold-rolled Fe-based metal plate recovers or recrystallizes, a texture oriented in the {100} direction is formed on the Fe-based metal plate.
When a magnetic field is applied in a direction perpendicular to the cold rolling direction (sheet thickness direction), a texture oriented in the {100} direction is formed in a direction parallel to the plate surface, and the magnetic field is parallel to the cold rolling direction. When applied in the direction (long direction of the plate), a texture oriented in the {100} direction in the direction perpendicular to the plate surface is formed. For this reason, when a magnetic field is applied in both directions, a texture oriented in the {100} direction is formed in two directions, a direction parallel to the plate surface and a direction perpendicular to the plate surface.

Although the detailed mechanism by which such a texture is formed is not clear, during recovery or recrystallization, in addition to the energy stored during cold rolling, the energy of the magnetic field is used as the driving force to rotate or crystallize the crystal. Can be considered. As an action of the magnetic field, the crystal is rotated or crystallized with a preferential orientation such that the direction in which the magnetic field is applied and the direction of easy magnetization are parallel. In the Fe-based metal plate, since the easy axis of magnetization is <100>, the surface perpendicular to the magnetic field application direction tends to be {100}.
As a result, when a magnetic field is applied in a direction perpendicular to the rolling direction, a {100} texture is formed parallel to the rolling direction, and when a magnetic field is applied in a direction parallel to the rolling direction, {100} assembly is perpendicular to the rolling direction. An organization is considered to be formed.

The magnetic field applied to form the magnetic field may be a static magnetic field or an alternating magnetic field. As a method for applying the magnetic field, a well-known ordinary method may be used. In order to apply a magnetic field perpendicular to the rolling direction, there is a method of arranging a magnet so as to face each rolling surface of the base metal plate. To apply a magnetic field parallel to the rolling direction, a direct current or an alternating current is applied. There is a method of arranging a base metal plate in a flowed coil.
The strength of the magnetic field to be applied is preferably 0.01 T or more and 10 T or less in terms of magnetic flux density when the magnetic field is applied perpendicular to the rolling direction. If it is less than 0.01T, it is difficult to make the {200} plane integration degree 20% or more. Above 10T, the effect is saturated.
Moreover, when applying a magnetic field in parallel with a rolling direction, 0.2T or more and 10T or less are preferable at a magnetic flux density for the same reason.

({200} surface integration degree)
By applying a magnetic field under the conditions as described above, a region in which the {200} plane integration degree in the rolling direction is increased or 2 in the plate thickness direction and the rolling direction are applied to a part or the entire region of the base metal plate. A region having an increased degree of {200} plane integration in the direction is formed. The {200} plane integration degree in the region is preferably 20% or more and 60% or less. If the degree of integration is less than 20%, it is difficult to make the {200} plane integration degree 30% or more after diffusion heat treatment, and if it exceeds 60%, the magnetic properties are saturated after heat diffusion heat treatment.

In addition, the measurement of the plane integration degree of the azimuth plane can be performed by X-ray diffraction using MoKα rays.
More specifically, for each sample, there are 11 orientation planes ({110}, {200}, {211}, {310}, {222}, {321}, which are 11 α-Fe crystals parallel to the sample surface. {411}, {420}, {332}, {521}, {442}) are measured, and each measured value is divided by the theoretical integrated strength of a sample in a random orientation, and then {110} Alternatively, the {222} strength ratio is obtained as a percentage.

In that case, for example, {110} intensity ratio is expressed by the following formula (I).
{200} plane integration degree = [{i (110) / I (110)} / Σ {i (hkl) / I (hkl)}] × 100 (I)
However, the symbols are as follows.
i (hkl): Measured integrated intensity of {hkl} plane in the measured sample I (hkl): Theoretical integrated intensity of {hkl} plane in the sample with random orientation Σ: Sum of 11 orientation planes of α-Fe crystal Here, the integrated intensity of a sample having a random orientation may be obtained by preparing a sample and actually measuring it.

The heat diffusion treatment present invention, the ferrite forming elements as dissimilar metals, for example is allowed and the base metal plate attached to Al, A _3-point of the base metal plate (e.g., a pure iron 910 ° C.) was heated to, preform Al is diffused into a part or the whole of the {100} texture region formed on the metal plate and alloyed with the base material.
Hereinafter, an example of a case where a base metal plate in which a {100} texture is formed in the rolling direction by applying a magnetic field in the plate thickness direction will be described in terms of changes when dissimilar metals diffuse. Even when a base metal plate in which {100} texture is formed in two directions of the rolling direction and the plate thickness direction by applying a magnetic field in the plate thickness direction and the rolling direction is basically the same. It is.

In the region where Al is alloyed, an α single-phase component is formed, and in that region, the γ phase is transformed into the α phase. First, when a base metal plate having a {100} texture is used, the transformation is carried out by taking over the orientation of the already formed {100} texture when transforming from the γ phase to the α phase. Therefore, a structure oriented in {100} is formed even in the alloyed region.
As a result, in the alloyed region, the {200} plane integration degree of the α-Fe phase is 25% or more and 99% or less, and the {222} plane integration degree is 0.1% or more and 40% or less accordingly. Tissue is formed.

  In addition, when a base metal plate on which a {100} texture is not formed is used, a magnetic field is applied as described above in the heating process of the heating diffusion process. Thereby, as the temperature rises, crystal grains oriented in {100} are formed. In addition, Al diffusion also occurs at the same time, and when the transformation from the γ phase to the α phase takes place, the transformation takes over the orientation of the {100} texture. It is formed.

Base metal plate further heated to a temperature of 1300 ° C. or less than _three points A, hold. Thereby, the {200} plane integration degree of the entire Fe-based metal plate is further increased as shown in FIG.
Area heating temperature is not the α single phase components exceeding _three points A is transformed gamma. In addition, since it has an α single-phase structure that does not undergo γ transformation in the already alloyed region, the {100} crystal grains are preserved as they are, and {100} grains preferentially grow in that region and {200 } The degree of surface integration increases.
When the holding time is lengthened, {100} grains grow preferentially due to grain engagement. As a result, the {200} plane integration degree further increases. In addition, with the diffusion of Al, the region transformed into an Fe—Al alloy transforms from the γ phase to the α phase. At that time, α grains already oriented in {100} are formed in the region adjacent to the region to be transformed, and when transforming from the γ phase to the α phase, the transformation takes place in the form of taking over the crystal orientation of the adjacent α grains. As a result, the holding time becomes longer and the {200} plane integration degree increases. Further, as a result, the {222} plane integration degree decreases (the state shown in FIG. 2A).

In order to finally obtain a higher {200} plane integration degree of 50% or more, the holding time is adjusted, and at this stage, the {200} plane integration degree of the α-Fe phase is 30% or more. In addition, it is preferable that the {222} plane integration degree is 30% or less.
Also, if the entire sheet is held by the A ₃ point or higher until the alloying becomes α single-phase structure to the plate center, grain structure oriented in the {100} reaches the plate center. (State of Fig. 2-c)

In heat diffusion treatment, the case of applying a magnetic field, Atsushi Nobori rate of raising the temperature to _{3 A} is preferably not more than 0.1 ° C. / sec or higher 500 ° C. / sec. {200} plane oriented buds are efficiently formed at a temperature rising rate within this range. The same applies to the rate of temperature rise when no magnetic field is applied.
The holding temperature after the temperature rise is preferably ₃ points or more and 1300 ° C. or less. Even if it is heated at a temperature exceeding 1300 ° C., the effect on the magnetic properties is saturated. The heating and holding time may start cooling immediately after reaching the holding temperature (substantially hold for 0.01 seconds or more), or may be held for 600 minutes or less to start cooling. The effect is saturated even if it is kept for more than 600 minutes.
When this condition is satisfied, the accumulation of {200} plane-oriented buds further proceeds, and the {200} plane accumulation degree of the α-Fe phase can be set to 30% or more after cooling more reliably.

After cooling diffusion treatment after heating diffusion treatment, when the region where Al is not alloyed remains and is cooled, the non-alloyed region is already oriented to {100} during the transformation from γ to α. Transformed to take over the crystal orientation of the region, the {200} plane integration degree is increased, the {200} plane integration degree of the α-Fe phase is 30% or more and 99% or less, and { 222} A metal plate having a texture with a surface integration degree of 0.01% or more and 30% or less is obtained (state shown in FIG. 2B).
Further, as shown in FIG. 2C, when the grain structure that is held at A ₃ points or more and is oriented to {100} reaches the center of the plate until the whole plate is alloyed, it is cooled as it is and {100 }, A texture in which the grain structure oriented to the center of the plate is obtained. (State of Fig. 2-d)

Thereby, the dissimilar metal is alloyed on the entire plate, the {200} plane integration degree of the α-Fe phase is 30% or more and 99% or less, and the {222} plane integration degree is 0.01% or more and 30% or less. A metal plate having the following texture is obtained.
{200} surface residual state of dissimilar metals integration values and base metal sheet surface varies by A ₃ point or more holding time and holding temperature, in FIG. 2b, grain structure oriented in the {100} is Although it does not reach the center of the plate and the dissimilar metal remains on the surface, a grain structure oriented {100} to the center of the plate can be used, and the entire second layer on the surface can be alloyed.

  In the cooling after the diffusion treatment, the cooling rate is preferably 0.1 ° C./sec or more and 500 ° C./sec or less. When cooled in this temperature range, the growth of {200} plane oriented buds further proceeds.

Hereinafter, the present invention will be described in more detail by way of examples.
Example 1
In this example, pure iron is applied to the base material and Al is applied to the second layer, and the results of examining the relationship between the manufacturing conditions and the {200} plane integration degree are shown.

The material used as a base material was pure iron, and other components contained C: 0.0001%, Si: 0.0001%, Al: 0.0002%, and unavoidable impurities in mass%. This base material is obtained by melting an ingot by vacuum melting, hot rolling it, and then processing it to a predetermined thickness by cold rolling.
In hot rolling, an ingot having a thickness of 230 mm heated to 1000 ° C. was thinned to a thickness of 50 mm. After cutting a plate material of various thicknesses from this hot-rolled plate by machining, a base material was obtained by cold rolling at various cold rolling rates. As a result, the thickness of the obtained base material was in the range of 10 μm to 800 μm.
When the structure of the obtained cold-rolled sheet was observed, the main phase of the base material at room temperature was an αFe phase. A _3-point to cause alpha-gamma transformation was the result 911 ° C. of the measurement.

  Each base material was coated with Al as a second layer by ion plating (hereinafter referred to as IP method) or hot dipping method. The film thickness of 0.06 μm (total on both sides) was performed by the IP method, and the others were performed by the hot dipping method. These thicknesses are values measured on only one side.

Next, an experiment was performed in which the base metal plate to which the second layer was adhered was subjected to heat treatment under various conditions. A gold image furnace was used for heat treatment, and various heating rates and holding times were controlled by program control. The temperature raising and holding were performed in an atmosphere evacuated to a level of 10 ⁻³ Pa. Further, a magnetic field was applied perpendicularly to the rolling direction of the base metal plate during the temperature raising process.
When cooling the base metal plate, Ar gas was introduced and the cooling rate was controlled by adjusting the flow rate.

  For the formation of {100} -oriented buds (seeding) in the temperature raising process, the storage and high integration of {100} -oriented grains in the holding process, and the base metal of the same matrix-Al coating condition combination in the cooling process Three plates were prepared, and heat treatment experiments were performed for each process to examine changes in texture.

Samples relates seeding Atsushi Nobori process, and heated from room temperature to the base metal plate at a predetermined heating rate up to 911 ° C. is a _3-point A, also, in some samples were heated to 890 ° C., without holding time It was produced by cooling to room temperature. In the temperature range of 200 to 800 ° C. in the heating process, a 1.2 T magnetic field was applied perpendicular to the rolling direction of the sample. The cooling rate was 100 ° C./sec. The texture was measured by the X-ray diffraction method described above. X-rays were irradiated from the surface, and the {200}, {222} plane integration degree of the α-Fe phase was determined.

  The sample relating to storage and high integration in the holding process was prepared by heating the base metal plate in the same manner as the sample for seeding, and cooling to room temperature after a holding time of 10 seconds. Here, the cooling rate was 100 ° C./sec. The texture was measured by the X-ray diffraction method described above. X-rays were irradiated from the surface, and the {200}, {222} plane integration degree of the α-Fe phase was determined.

Samples related to growth in the cooling process were prepared in the same manner as samples related to storage and high integration. In order to evaluate the degree of {200} and {222} plane integration at the unalloyed position, the layers from the surface of the prepared sample to a predetermined distance are removed so that the unalloyed position becomes the evaluation surface. A test piece was prepared. When the whole plate was alloyed, the position was 1/2 t of the plate thickness.
The texture is measured by the X-ray diffraction method described above, and X-rays are irradiated from the surface of the test piece and a predetermined surface of the test piece from which the layer has been removed, respectively, and the {alpha} -Fe phase { 200}, {222} plane integration degree was determined.

The obtained product was evaluated by magnetic measurement. First, a magnetic flux density B50 with respect to a magnetizing force of 5000 A / m was determined using SST (Single Sheet Tester). At this time, the measurement frequency was 50 Hz. Next, the saturation magnetic flux density Bs was determined using a VSM (Vibrating Sample Magnetometer). The magnetizing force applied at this time was 0.8 × 10 ⁶ A / m. The evaluation value was the ratio B50 / Bs of B50 to the saturation magnetic flux density.

The alloying ratio of the second layer and the ratio of the α single phase region were determined and defined as follows.
In the L cross-section, the surface distribution of Fe content and the surface content of Al content were measured using EPMA (Electron Probe Micro-Analysis) method in the L direction 1 mm × total thickness field of view.
The alloying ratio of the second layer is the area when Fe ≦ 0.5 mass% and Al ≧ 99.5 mass% before and after heat treatment, and the area when Al is coated and not subjected to heat treatment. S0, where the area of the product after completion of all heat treatments is S, the alloying rate of the second layer is defined as (S0−S) / S0 × 100.
The ratio of the α single phase region was defined as (T / T0) × 100, where T0 is the area of the metal plate cross section after heat treatment observed in the L cross section and T is the area of the dissimilar metal diffusion region after heat treatment. When the second layer is Al, T is the area of the region where Al ≧ 0.9 mass%.

  Tables 1 and 2 show the conditions of the base metal plate, the heat treatment conditions, the {200} plane integration degree and the {222} plane integration degree measured in each process during and after manufacture. Moreover, the alloying ratio of the second layer of the obtained product metal plate, magnetic measurement evaluation results, and the like are shown.

As shown in Tables 1 and 2, in the examples of the present invention, a product metal plate in which the {200} plane integration degree of the α-Fe phase is 30% or more and the {222} plane integration degree is 30% or less is obtained. In addition, it can be confirmed that the metal plate has excellent magnetic properties with a B50 / Bs value of 0.88 or more.
In addition, as shown in Tables 1 and 2, such a metal plate is formed by adhering another metal to a metal plate made of pure iron to form a second layer, which is heated to a temperature of ₃ points or more. By applying a heat treatment for cooling and applying a magnetic field in the heating temperature raising process, the {200} plane of the α-Fe phase is highly integrated at each stage of the heat treatment, and the product metal plate of the present invention example is obtained. I can confirm that.
Furthermore, in the present invention example, excellent magnetic properties in a range of a wide range of alloying ratio and α single-phase region ratio based on the combination of the base metal plate and the second layer thickness, the heating rate, the heating holding temperature and holding time It can be confirmed that a product metal plate is obtained.
On the other hand, No. 2 which does not use the metal of the second layer even when heat treatment is performed by heating and cooling while applying a magnetic field. No. 1 or A. No. No heating to a temperature of ₃ points or more. In the example 2, a metal plate having a high {200} plane integration degree as in the example of the present invention cannot be obtained, and as a result, the obtained magnetic characteristics are also inferior.

(Example 2)
In this embodiment, an Fe-based metal plate is applied to the base material, and Si, Sn, Ti, W, Ga, Zn, Ge, Cr, Mo, Sb, V, and 92Al8Si (mass%) alloy are applied to the second layer. The result of having investigated about the relationship between manufacturing conditions and {200} plane integration degree is shown.

Seven types of component systems A to G were prepared as the Fe-based metal plate serving as a base material, and specific components are shown in Table 3. In manufacturing these base materials, an ingot is melted by vacuum melting, hot-rolled, and then processed into a predetermined thickness by cold rolling.
In hot rolling, an ingot having a thickness of 230 mm heated to 1000 ° C. was thinned to a thickness of 50 mm. After cutting a plate material of various thicknesses from the hot-rolled plate by machining, cold rolling at various cold rolling rates was performed to produce base metal plates of various thicknesses. As a result, the thickness of the obtained base material was in the range of 10 μm to 700 μm.
When the structure of the obtained cold-rolled sheet was observed, the main phase of any base material at room temperature was the αFe phase. Also showed A ₃ point to cause alpha-gamma transformation to the measured Table 3.

As a method of coating each base material with Si, Sn, Ti, W, Ga, Zn, Ge, Cr, Mo, Sb, V, and 92Al8Si alloy as a second layer, a hot dipping method, a vapor deposition method (IP method, Sputtering method) was applied. Then, Sn and Zn were coated by a hot dipping method, and other metals were coated by a vapor deposition method.
Tables 4 and 6 show the thicknesses of the films of the different kinds of metals as the total of both surfaces of the base material.

Subsequently, heat treatment was performed under various conditions by the same method used in Example 1 except for the application time of the magnetic field, and an experiment was performed to evaluate the state in each process during production.
Invention Examples 53, 54, 55, 56, 58, 59, 60, 61, 64, 65, 66, 67, 70, 71, 72, and Comparative Examples 51, 52, 56, 57, 62, 63, 68 69, before coating the second layer, heat treatment is performed by applying a magnetic field at 200 to 800 ° C., and then cooling to room temperature, after which the second layer coating is formed and then heat-treated. It has been seeded. The other comparative examples and the inventive examples were stored, integrated and grown in the same order as in Example 1.

Here, the alloying ratio of the second layer and the ratio of the α single phase region were determined as follows.
In the alloying ratio of the second layer, when the metal element of the second layer is [M], in any element, the region where Fe ≦ 0.5 mass% and [M] ≧ 99.5 mass% is satisfied. The area was determined. The area in the case where the element of the second layer is coated and not heat-treated is S0, the area in the product after all the heat treatment is S, and the alloying ratio of the second layer is (S0-S) / S0. It calculated | required from * 100.
The ratio of the α single phase region was defined as (T / T0) × 100, where T0 is the area of the metal plate cross section observed in the L cross section and T is the area of the dissimilar metal diffusion region after the heat treatment. When the second layer was Si, T was obtained from the area of the region where Si ≧ 1.9 mass%. Similarly, in the case of Sn, a region where Sn ≧ 3.0 mass%, in the case of Ti, a region where Ti ≧ 3.0 mass%, in the case of W, a region where W ≧ 6.6 mass%, In the case of Ga, a region where Ga ≧ 4.1 mass%, in the case of Zn, a region where Zn ≧ 7.2 mass%, in the case of Ge, a region where Ge ≧ 6.4 mass%, Cr In the case of Cr ≧ 14.3 mass%, in the case of Mo, in the case of Mo ≧ 3.8 mass%, in the case of Sb, in the region of Sb ≧ 3.6 mass%, in the case of V Is a region where V ≧ 1.8 mass%. In the case of 92Al8Si alloy, Al ≧ 0.9 mass% and Si ≧ 0.1 mass. The area of each region to be% was obtained.

  Tables 4 to 7 show the conditions of the base metal plate, the heat treatment conditions, the {200} plane integration degree and the {222} plane integration degree measured in each process during the manufacturing and after the manufacturing. Moreover, the alloying ratio of the second layer of the obtained product metal plate, magnetic measurement evaluation results, and the like are shown.

As shown in Tables 4 to 7, in the examples of the present invention, steels having various α-γ transformation chemical compositions were used, and in any case using various dissimilar metals, α-Fe phase {200 } A product metal plate satisfying the condition that the degree of surface integration is 30% or more and the degree of {222} surface integration is 30% or less is obtained, and the metal plate has a B50 / Bs value of 0.87 or more. It can be confirmed that excellent magnetic properties are obtained.
Also, such metal plate, as shown in Table 4-7, the base metal plate which has been subjected to pre-magnetic field during the heat treatment, the second layer is formed by deposition of other metals, it A ₃ points by heat treatment of cooling and heating to a temperature above or the second layer and the formed base metal plate of a magnetic field was applied during heating to a temperature of at least _three points a, cooled and then cooled By performing the heat treatment, it can be confirmed that the {200} plane of the α-Fe phase is highly integrated in each stage of the heat treatment, and the product metal plate of the present invention example is obtained.
Furthermore, in the present invention example, excellent magnetic properties in a range of a wide range of alloying ratio and α single-phase region ratio based on the combination of the base metal plate and the second layer thickness, the heating rate, the heating holding temperature and holding time It can be confirmed that a product metal plate is obtained.
On the other hand, No. 2 which does not use the metal of the second layer even when heat treatment is performed by heating and cooling while applying a magnetic field. No. 29, 35, 41, 46, 51, 57, 62, 68, 73, 79, 85, 90, A No. No heating to a temperature of ₃ points or more. In the examples of 30, 36, 42, 47, 52, 58, 63, 69, 74, 80, 86, 91, a metal plate having a high {200} plane integration degree as in the present invention example cannot be obtained, and as a result, The obtained magnetic properties are also inferior.

(Example 3)
In Example 1, no. Under conditions of 1-3, 6, 8, 9, 13, 15, 17, 20, 21, 24, 25, each of manufacture of the base metal plate, adhesion of the second layer, seeding, storage high integration, growth When producing a product metal plate by performing the process, as a method of applying a magnetic field in the seeding process, in addition to applying perpendicularly to the rolling direction, a method of applying also in parallel to the rolling direction was performed.
Table 8 shows a part of the manufacturing conditions used in Example 1 with the addition of the magnitude of the magnetic field applied in parallel to the rolling direction and the temperature range to which the magnetic field is applied, and the thickness direction and the plate surface measured after the manufacturing. The {200} plane integration degree and {222} plane integration degree in the parallel direction (rolling direction) and the magnetic measurement evaluation results are shown. In Table 8, “a” is added to the corresponding No in Example 1 such as 1a, 2a. It was.

As shown in Table 8, in the example of the present invention, the {200} plane integration degree in the plate thickness direction and the rolling direction of the α-Fe phase is both 30% or more and 99% or less, and the {222} plane integration degree. From 0.01% to 30%, it was confirmed that an excellent magnetic property steel plate having a B50 / Bs value of 0.87 or more in the two directions of the plate thickness direction and the rolling direction was obtained.
On the other hand, No. 2 which does not use the metal of the second layer even when heat treatment is performed by heating and cooling while applying a magnetic field from two directions. No. 1a or A. No heating to a temperature of ₃ points or higher. In the example of 2a, a metal plate having a high {200} plane integration degree in two directions as in the present invention example cannot be obtained, and as a result, the obtained magnetic properties are also inferior.

Example 4
31, 33, 37, 39, 42, 45, 48, 50, 53, 56, 59, 61, 64, 67, 70, 72, 75, 78, 81, 84, 87, 89, 92, of Example 2. When producing a product metal plate under the conditions of 94, as a method of applying a magnetic field in the seeding process, in addition to applying perpendicularly to the rolling direction, a method of applying also in parallel to the rolling direction as in Example 3 was performed. It was.
In Table 9, the magnitude of the magnetic field applied in parallel to the rolling direction and the temperature range in which the magnetic field was applied are shown as part of the manufacturing conditions used in Example 2. Table 10 shows the {200} plane integration degree and {222} plane integration degree in the sheet thickness direction and the rolling direction measured after manufacture, and the magnetic measurement evaluation results. In addition, No of Example was attached | subjected similarly to Table 8.
As shown in Table 10, in the example of the present invention, the {200} plane integration degree in the plate thickness direction and the rolling direction of the α-Fe phase are both 30% or more and 99% or less, and the {222} plane integration degree. There becomes less than 30% 0.01%, the value of B50 / Bs is, it was confirmed that the thickness direction and excellent magnetic properties steel sheet 0.8 6 or more in two directions in the rolling direction can be obtained.

  The Fe-based metal plate of the present invention is suitable for a magnetic core such as a transformer in which a silicon steel plate is used, and can contribute to miniaturization of these magnetic cores and reduction of energy loss.

Claims (4)

A method for producing an Fe-based metal plate having a high degree of {200} plane integration,
(A 1 ) a step of preparing a base metal plate made of an α-γ transformation component Fe-based metal and having a processed structure ;
(A2) attaching a ferrite-forming element to one side or both sides of the prepared base metal plate;
(B) the attached base metal plate ferrite forming element, and heated to ₃ A base material while applying a magnetic field at the Curie temperature or less, the diffusion of ferrite forming elements in a part or all of the base metal plate And alloying step,
(C) The base metal plate is heated and held at a temperature of A ₃ or higher and 1300 ° C. or lower to increase the {200} plane integration degree of the α-Fe phase alloyed by the diffusion of the ferrite-forming elements { 222} reducing the degree of surface integration;
(D) the base metal plate is cooled to a temperature of A less than ₃ points, when the gamma-Fe phase in the region not alloyed is transformed to alpha-Fe phase, the region {200} plane integration of 30 % Of the Fe-based metal having a high {200} plane integration characterized by having a step of adjusting the {222} plane integration degree to 0.01% or more and 30% or less. A manufacturing method of a board. 2. The method for producing an Fe-based metal plate according to claim 1, wherein, instead of the steps (a2) and (b), the following (e) while applying a magnetic field to the prepared base metal plate, the Fe A step of performing a heat treatment for heating to a Curie temperature (° C.) ± 50 ° C. of the base metal;
(F) attaching a ferrite-forming element to one or both surfaces of the base metal plate after the heat treatment;
The deposited metal plate (g) ferrite forming element and heated to ₃ A base material, some or all of the base metal plate to diffuse the ferrite forming elements, as engineering for alloying
Method of manufacturing a Fe-based metal plate having a high {200} plane integration characterized by having and.   3. The Fe-based metal plate having a high degree of {200} plane integration according to claim 1, wherein a magnetic field having a magnetic flux density of 0.01 T or more is applied to the base metal plate perpendicularly to the rolling direction. Manufacturing method.   A magnetic field having a magnetic flux density of 0.01 T or more is applied to the base metal plate perpendicularly to the rolling direction, and a magnetic field having a magnetic flux density of 0.2 T or more is applied in parallel to the rolling direction. The manufacturing method of the Fe-type metal plate which has the high {200} plane integration degree of 1 or 2.

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