JPH03294468A - Production of grain-oriented silicon steel sheet having small iron loss - Google Patents
Production of grain-oriented silicon steel sheet having small iron lossInfo
- Publication number
- JPH03294468A JPH03294468A JP2096885A JP9688590A JPH03294468A JP H03294468 A JPH03294468 A JP H03294468A JP 2096885 A JP2096885 A JP 2096885A JP 9688590 A JP9688590 A JP 9688590A JP H03294468 A JPH03294468 A JP H03294468A
- Authority
- JP
- Japan
- Prior art keywords
- silicon steel
- steel sheet
- film
- grain
- oriented silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 43
- 229910052742 iron Inorganic materials 0.000 title abstract description 20
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 25
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000007747 plating Methods 0.000 claims abstract description 21
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- 238000007750 plasma spraying Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052839 forsterite Inorganic materials 0.000 abstract description 6
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 3
- 229960002163 hydrogen peroxide Drugs 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000007751 thermal spraying Methods 0.000 description 10
- 230000005381 magnetic domain Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021343 molybdenum disilicide Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910021358 chromium disilicide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JUYZUJLVHMHVIY-UHFFFAOYSA-N dioxido(oxo)silane;molybdenum(4+) Chemical compound [Mo+4].[O-][Si]([O-])=O.[O-][Si]([O-])=O JUYZUJLVHMHVIY-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating By Spraying Or Casting (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は鉄損値が極めて低い一方向性珪素鋼板の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a grain-oriented silicon steel sheet having an extremely low core loss value.
（従来の技術）
一方向性珪素鋼板は、磁気鉄芯として多用され、エネル
ギーロスを少なくすべく鉄損を低減することが要求され
る。而して、一方向性珪素鋼板の鉄損を低減する手段と
して、仕上焼鈍後の材料表面にレーザービームを照射し
て局部的な歪を与え、それによって磁区を細分化して鉄
損を低下させる方法がたとえば特開昭５８−２６４０５
号公報に開示されている。また、一方向性珪素鋼板を鉄
芯へ加工した後、歪取焼鈍（応力除去焼鈍）を施しても
磁区細分化効果が消失しない磁区細分化手段として、た
とえば特開昭６２−８６１７５号公報に開示されている
方法がある。これらの技術的手段によって一方向性珪素
鋼板の鉄損値を低下させることができるが、さらに鉄損
値の低減を図ろうとするときは仕上焼鈍後の材料表面に
存在するグラス皮膜を除去し、鋼板表面近傍の磁区の動
きを阻害する地鉄表面の凹凸を取り除くことが重要であ
る。そのための手段として、仕上焼鈍後の材料の地鉄表
面を鏡面仕上げするか、または、鏡面仕上げした材料表
面に金属めっきを施すという方法がある。さらには、前
記の鏡面仕上げし、金属めっきした材料表面に絶縁■を
塗布し焼付けることによって、超低鉄損の一方向性珪素
鋼板を得る方法が特公昭５２２４４９９号公報に提案さ
れてむ゛る。さらに、たとえば特開昭６１−２０１７３
２号公報には、表面の平均粗さが０．４ ｎ以下の鏡面
状態に仕上げた一方向性珪素鋼板を、Ｔｉを含むガスと
非酸化性ガスからなる雰囲気下に５００〜１０００°Ｃ
の温度域で熱処理し、表面にＴｉＮ 、 Ｔｉｃ 、
Ｔｉ（Ｃ，Ｎ）からなる極薄張力皮膜を形成し、さらに
絶縁皮膜を被覆することによって鉄損値の低い一方向性
珪素鋼板を得る方法が開示されている。(Prior Art) Unidirectional silicon steel sheets are often used as magnetic cores, and are required to reduce iron loss in order to reduce energy loss. Therefore, as a means to reduce the iron loss of unidirectional silicon steel sheets, a laser beam is irradiated onto the material surface after final annealing to give local strain, thereby subdividing the magnetic domains and lowering the iron loss. For example, the method is disclosed in Japanese Patent Application Laid-Open No. 58-26405.
It is disclosed in the publication No. In addition, as a magnetic domain refining means in which the magnetic domain refining effect does not disappear even if strain relief annealing (stress relief annealing) is applied after processing a unidirectional silicon steel plate into an iron core, for example, Japanese Patent Application Laid-Open No. 62-86175 discloses There is a method disclosed. These technical measures can reduce the iron loss value of unidirectional silicon steel sheets, but when attempting to further reduce the iron loss value, it is necessary to remove the glass film present on the material surface after final annealing. It is important to remove irregularities on the surface of the steel plate that inhibit the movement of magnetic domains near the surface of the steel plate. As a means for this purpose, there is a method of mirror-finishing the bare surface of the material after finish annealing, or applying metal plating to the mirror-finished material surface. Furthermore, Japanese Patent Publication No. 5224499 proposes a method of obtaining an ultra-low core loss unidirectional silicon steel sheet by coating and baking an insulating material on the surface of the mirror-finished and metal-plated material. Ru. Furthermore, for example, JP-A-61-20173
In Publication No. 2, a unidirectional silicon steel plate finished in a mirror-like state with an average surface roughness of 0.4 nm or less is heated at 500 to 1000°C in an atmosphere consisting of a Ti-containing gas and a non-oxidizing gas.
After heat treatment in the temperature range of
A method is disclosed in which a unidirectional silicon steel sheet with a low iron loss value is obtained by forming an ultra-thin tensile film made of Ti (C, N) and further covering it with an insulating film.
（発明が解決しようとする課題）
一方向性珪素鋼板の地鉄表面を鏡面仕上げし、ＣＶＤ、
ＰＶＤ或いはイオンブレーティングといった手段によっ
て皮膜を形成することが近来多く提案されている。これ
らの方法はそれなりの効果が認められるが、１０−５Ｔ
ｏｒｒ以下の真空を必要とし、厚い膜を形成するために
は長時間を要するので、生産性が極めて低くまた高いコ
ストを要する。(Problem to be solved by the invention) The base surface of the unidirectional silicon steel plate is mirror-finished, CVD,
Recently, many proposals have been made to form a film by means such as PVD or ion blating. Although these methods have some effectiveness, 10-5T
It requires a vacuum of less than orr or more and takes a long time to form a thick film, resulting in extremely low productivity and high costs.
本発明はこれら従来技術における問題を解決し、極めて
鉄損値の低い一方向性珪素鋼板を低いコストで工業的に
生産することができる製造プロセスを提供することを目
的としてなされた。The present invention has been made with the object of solving these problems in the prior art and providing a manufacturing process that can industrially produce unidirectional silicon steel sheets with extremely low iron loss values at low cost.
（課題を解決するための手段） 本発明の要旨とするところは下記のとおりである。(Means for solving problems) The gist of the present invention is as follows.
（１）仕上焼鈍後の一方向性珪素鋼板の平滑化した地鉄
表面に金属メッキを施した後、低圧プラズマ溶射法にて
珪化物皮膜を形成せしめることを特徴とする低鉄損一方
向性珪素鋼板の製造方法。(1) Low core loss unidirectionality characterized by applying metal plating to the smoothed base steel surface of the unidirectional silicon steel plate after finish annealing, and then forming a silicide film by low pressure plasma spraying. Method of manufacturing silicon steel plate.
（２）仕上焼鈍後の一方向性珪素鋼板の平滑化した地鉄
表面に金属メッキを施した後、低圧プラズマ溶射法にて
珪化物皮膜を形成せしめ、さらに張力付与膜を塗布焼付
けすることを特徴とする低鉄損一方向性珪素鋼板の製造
方法。(2) After applying metal plating to the smoothed base steel surface of the unidirectional silicon steel sheet after final annealing, a silicide film is formed using a low-pressure plasma spraying method, and a tension imparting film is further applied and baked. A method for manufacturing a unidirectional silicon steel sheet with a characteristic low core loss.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明者らは上記従来技術における問題を解決するため
に、低圧プラズマ溶射法によって一方向性珪素鋼板表面
に珪化物皮膜を形成することを考えた。従来の低圧プラ
ズマ溶射では噴射珪化物の粒径が５０〜１００ｎと大き
いため、形成される珪化物皮膜も１１００ｆ以上の極め
て厚いものとなってしまう。本発明者らは珪化物の粒径
を１２ｔｒｍ以下にするとともに、基板の温度を４００
’Ｃ以上にすることによって短時間で極めて密着性の
すぐれた１２４以下の厚さの皮膜を形成せしめ得ること
を見出した。In order to solve the problems in the prior art described above, the present inventors considered forming a silicide film on the surface of a unidirectional silicon steel plate by a low-pressure plasma spraying method. In conventional low-pressure plasma spraying, the particle size of the sprayed silicide is as large as 50 to 100n, so the silicide film formed is extremely thick, 1100f or more. The present inventors reduced the grain size of the silicide to 12 trm or less and lowered the temperature of the substrate to 400 trm.
It has been found that by increasing the thickness to 124 or more, it is possible to form a film with a thickness of 124 or less with extremely good adhesion in a short period of time.
しかしながら、直接平滑下地面に溶射を行うと、溶射粒
子の衝突により平滑面が粗らされるため磁区がピンニン
グされ磁気特性が悪くなる。そこで、種々の検討を行っ
た結果、平滑化した下地面に好ましくは厚さＩＩ！ｒｎ
以上の金属メッキを施した後、溶射を行えば磁気特性を
損なうことなく低圧プラズマ溶射皮膜が付与できるとい
う新知見を得た。However, when thermal spraying is performed directly on a smooth underlying surface, the smooth surface is roughened by collisions of sprayed particles, causing pinning of magnetic domains and deterioration of magnetic properties. Therefore, as a result of various studies, it is preferable to use a thickness of II! for the smoothed base surface. rn
We have obtained new knowledge that if thermal spraying is performed after the metal plating described above, a low-pressure plasma sprayed coating can be applied without impairing magnetic properties.
このようにして形成された皮膜を有する一方向性珪素鋼
板は磁気的特性が極めて優れている。A unidirectional silicon steel sheet having a film formed in this manner has extremely excellent magnetic properties.
本発明に従った低圧プラズマ溶射法による珪化物皮膜材
成手段は、仕上焼鈍後の材料表面のグラス皮膜を除去し
て地鉄表面を平滑に仕上げ、金属メッキを施した後、そ
の表面に珪化物皮膜を形成せしめるべく適用することが
できる。また、この手段は一方向性珪素鋼板をス） Ｉ
Ｊツブを走行させる状態下で二次再結晶させ、その後に
皮膜をつけるプロセスにも適用できるのは勿論である。The means for forming a silicide film by the low-pressure plasma spraying method according to the present invention is to remove the glass film on the surface of the material after final annealing to smoothen the surface of the steel, apply metal plating, and then apply silicification to the surface. It can be applied to form a material film. In addition, this means uses a unidirectional silicon steel plate.
Of course, it can also be applied to a process in which secondary recrystallization is performed while the J-tube is running, and then a film is applied.
さらに、特公昭６３−４４８０４号公報、特公昭６３−
６６１１号公報に開示されている、一方向性珪素鋼板を
鉄芯に加工した後歪取り焼鈍を施しても磁区細分化効果
が消失しない磁区制御技術と組み合わせて使用すること
もできる。In addition, Japanese Patent Publication No. 44804/1983, Japanese Patent Publication No. 63-44804,
It can also be used in combination with the magnetic domain control technology disclosed in Japanese Patent No. 6611, in which the magnetic domain refining effect does not disappear even if a unidirectional silicon steel plate is processed into an iron core and then subjected to strain relief annealing.
以下に本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
４ｗｔ％以下のＳｉを含有する綱スラブを加熱し、熱間
圧延して熱延板とし、必要に応じてこの段階で焼鈍を施
し、次いで１回或は中間焼鈍を介挿する２回の冷間圧延
を施して最終板厚とした後、脱炭焼鈍し焼鈍分離剤を塗
布してストリップコイルとし、ついで高温長時間の仕上
焼鈍を施し、（１１０）＜００１＞方位の二次再結晶粒
を発達させた鋼板のフォルステライト皮膜を、化学的或
いは機械的に除去するかまたは、前記焼鈍分離剤をアル
ミナ等のフォルステライト皮膜を形成しないものにして
仕上焼鈍後の鋼板表面の地鉄を露出させ、弗酸と過酸化
水素を含む溶液中に浸漬するか或いは電解研磨によって
地鉄表面を平滑化した後、金属メッキを施し、低圧プラ
ズマ溶射装置中で珪化物皮膜を形成する。A steel slab containing 4 wt% or less of Si is heated and hot-rolled into a hot-rolled sheet, annealed at this stage if necessary, and then cooled once or twice with intermediate annealing. After rolling to achieve the final plate thickness, decarburization annealing is applied and an annealing separator is applied to form a strip coil, followed by finishing annealing at high temperature for a long time to obtain secondary recrystallized grains with (110)<001> orientation. Chemically or mechanically remove the forsterite film on the steel plate that has developed or use a material such as alumina that does not form a forsterite film as the annealing separator to expose the base iron on the surface of the steel plate after finish annealing. After smoothing the surface of the base metal by immersing it in a solution containing hydrofluoric acid and hydrogen peroxide or by electrolytic polishing, metal plating is applied, and a silicide film is formed in a low-pressure plasma spraying device.
金属メッキを施す意味は、プラズマ溶射の粒子衝突によ
る下地面のダメージを防止するためである。金属メッキ
は、そのメッキ金属、メッキ方法において特に限定され
ることはないが、Ｚｎ、 Ｓｎ。The purpose of applying metal plating is to prevent damage to the underlying surface due to particle collision during plasma spraying. Metal plating is not particularly limited in terms of the plating metal or plating method, but Zn and Sn may be used.
Ｃｕ、 Ｎｉ等の金属メッキを行うのが最も実用的であ
る。通常のプラズマ溶射条件では１ｍ＋前後の下地の凹
凸が生じ、交流磁場中での磁区の動きをピンニングする
ので鉄損が損なわれる。これを防止するために好ましく
は厚さ１−以上のメッキを施した後に低圧プラズマ溶射
するのが効果的である。It is most practical to perform metal plating such as Cu or Ni. Under normal plasma spraying conditions, irregularities occur on the base of around 1 m+, which pinning the movement of magnetic domains in an alternating magnetic field, impairing iron loss. To prevent this, it is effective to perform low-pressure plasma spraying after plating to a thickness of preferably 1 mm or more.
下地面を金属メッキで保護して、低圧プラズマ溶射皮膜
で下地に大きな張力を付与して極めて磁性の良い製品を
得るのが本発明の目的である。The object of the present invention is to protect the underlying surface with metal plating and apply a large tension to the underlying surface with a low-pressure plasma spray coating to obtain a product with extremely good magnetic properties.
以下に本発明の実施に用いた低圧プラズマ溶射条件の一
例を示す。An example of low pressure plasma spraying conditions used in carrying out the present invention is shown below.
作動ガス ：Ａｒ＋Ｈｔ 入力 ：８５ＫＷ 溶射雰囲気圧カニ ６０Ｔｏｒｒ 溶射距離 ：４５０ｍｍ 粉体供給速度 ： ４４ ｇ ／ｌ１ｌｉｎ。Working gas: Ar+Ht Input: 85KW Thermal spray atmospheric pressure crab 60 Torr Spraying distance: 450mm Powder supply rate: 44 g/l1lin.
なお、本発明は上記溶射条件に限定されるものではない
。Note that the present invention is not limited to the above thermal spraying conditions.
第１図は噴射粉末に二珪化モリブデン（ＭｏＳｉｚ）を
用いた時の二珪化モリブデン平均粒径と溶射厚みの関係
を示したものである。この図かられかるように、噴射珪
化物（溶射物粉末）の粒径を小さくするほど同一溶射時
間で薄い皮膜を形成できる。FIG. 1 shows the relationship between the average particle diameter of molybdenum disilicide (MoSiz) and the spray thickness when molybdenum disilicide (MoSiz) is used as the spray powder. As can be seen from this figure, the smaller the particle size of the sprayed silicide (spray powder), the thinner the coating can be formed in the same spraying time.
次に、溶射時の珪素鋼板（基板・・・Ｓｎメッキあり）
の温度と溶射後の溶射皮膜の密着性について調べた結果
を、第２図に示す。第２図から明らかなように基板の温
度を室温から漸次上昇させていくに従い溶射皮膜の密着
性が向上する。これは溶射時に基板の温度を高くしてお
くことによって、溶融した溶射材料液滴と基板との濡れ
性が改善されるとともに拡散が起こることによるものと
考えられる。Next, silicon steel plate (substrate...with Sn plating) during thermal spraying
Figure 2 shows the results of an investigation of the temperature and adhesion of the sprayed coating after thermal spraying. As is clear from FIG. 2, as the temperature of the substrate is gradually raised from room temperature, the adhesion of the sprayed coating improves. This is thought to be due to the fact that by keeping the temperature of the substrate high during thermal spraying, the wettability between the melted thermal spray material droplets and the substrate is improved and diffusion occurs.
溶射皮膜の密着性は溶射後の珪素鋼板を３０ｍｍφの丸
棒に巻き付けたときの溶射皮膜の剥離率で評価した。第
２図から明らかなごとく基板の温度を４００°Ｃ以上に
すると、溶射皮膜の密着性が良好となる（剥離率が低下
する）。４００°Ｃ以上の基板温度で、通常のフォルス
テライト皮膜の密着性と同等の密着性を示している
溶射に用いる粉体はチタン（Ｔｉ）、ジルコニラＬ、
（Ｚｒ） 、ニオブ（Ｎｂ） 、タンタル（Ｔａ） 、
クロム（Ｃｒ） 、モリブデン（Ｍｏ） 、タングステ
ン（Ｗ）等の二珪化物単体あるいは、これらの混合物、
さらに珪素の結合割合の異なる化合物（たとえばＭｏ３
Ｓｉ３）のいずれでもよいが、製品の鉄構向上を考える
場合は、下地の珪素鋼板（地鉄）との間で熱膨張係数の
差の大きな珪化物を用いた方が下地に大きな張力が付与
され鉄損が向上する。珪化物皮膜の形成後、−旦下地を
８００℃程度に加熱して下地と珪化物皮膜の歪の緩和を
行った方が鉄損が向上する。珪化物皮膜の形成後、鋼板
に張力皮膜を塗布し焼付ける場合は、焼付けが８００°
Ｃ以上の温度域でなされるから、下地と珪化物皮膜の歪
の緩和が併せて行われる。製品を巻鉄芯等に加工した後
、８００°Ｃ以上の温度域で歪取り焼鈍を行う場合にも
、下地と珪化物皮膜の歪の緩和が併せて行われる。The adhesion of the thermal sprayed coating was evaluated by the peeling rate of the thermal sprayed coating when the silicon steel plate after thermal spraying was wound around a 30 mmφ round bar. As is clear from FIG. 2, when the temperature of the substrate is 400° C. or higher, the adhesion of the sprayed coating becomes better (the peeling rate decreases). The powders used for thermal spraying, which exhibit adhesion equivalent to that of ordinary forsterite films at substrate temperatures of 400°C or higher, include titanium (Ti), zirconia L,
(Zr), niobium (Nb), tantalum (Ta),
Single disilicides such as chromium (Cr), molybdenum (Mo), and tungsten (W), or mixtures thereof,
Furthermore, compounds with different silicon bonding ratios (for example, Mo3
Any type of Si3) may be used, but when considering improving the steel structure of the product, it is better to use a silicide that has a large difference in coefficient of thermal expansion from the underlying silicon steel plate (substrate) because it will impart greater tension to the underlying material. iron loss is improved. After the silicide film is formed, the core loss is improved by heating the base to about 800° C. to relax the strain between the base and the silicide film. After forming the silicide film, when applying the tension film to the steel plate and baking it, the baking angle should be 800°.
Since this is done in a temperature range of C or higher, the strain on the base and the silicide film is also relaxed. Even when strain relief annealing is performed in a temperature range of 800° C. or higher after processing the product into a wound iron core or the like, the strain on the base and the silicide film is also relaxed.
（実施例）
実施例Ｉ
Ｓｉ：３．２％を含む板厚０．３ｍｍの仕上焼鈍後の高
磁束密度一方向性珪素鋼板を硫酸と弗酸の混合物に浸漬
してフォルステライト皮膜を除去した後、弗酸と過酸化
水素を含む溶液中で地鉄表面を平滑にし鏡面に仕上げた
。鏡面仕上げ後、この鋼板を低圧プラズマ溶射装置に導
入し、基板温度を５００°Ｃとして平均粒径１１−アン
ダー〇〇二珪化クロムを溶射して７ｉｎＢ厚さの珪化物
皮膜を形成した。(Example) Example I A finish annealed high magnetic flux density unidirectional silicon steel plate containing 3.2% Si and having a thickness of 0.3 mm was immersed in a mixture of sulfuric acid and hydrofluoric acid to remove the forsterite film. Afterwards, the surface of the steel base was smoothed into a mirror finish in a solution containing hydrofluoric acid and hydrogen peroxide. After mirror finishing, this steel plate was introduced into a low-pressure plasma spraying apparatus, and chromium disilicide with an average particle size of 11-under was sprayed at a substrate temperature of 500°C to form a silicide film with a thickness of 7 inB.
その後、不活性ガス雰囲気下、８００″Ｃに加熱して歪
の緩和を行った。こうして得られた製品の鉄損値を第１
表に示す。Thereafter, the strain was relaxed by heating to 800"C in an inert gas atmosphere.The iron loss value of the product thus obtained was
Shown in the table.
第１表
このように、本発明法は従来技術に比較して鉄損値が格
段に向上している。Table 1 As shown, the method of the present invention has a significantly improved iron loss value compared to the conventional technology.
実施例２
Ｓｉ ： ３．２％を含む板厚０．３ ｍｍの仕上焼鈍
後の高磁束密度一方向性珪素鋼板のフォルステライト皮
膜を砥石によって機械的に除去した後、弗酸と過酸化水
素を含む溶液中で地鉄表面を平滑にし鏡面に仕上げた。Example 2 After mechanically removing the forsterite film of a high magnetic flux density unidirectional silicon steel plate containing 3.2% Si and finishing annealing with a thickness of 0.3 mm using a grindstone, hydrofluoric acid and hydrogen peroxide were removed. The surface of the steel base was smoothed and finished to a mirror surface in a solution containing .
鏡面仕上げ後、３ＪｎＢのクロムメッキを施した後、こ
の鋼板を低圧プラズマ溶射装置に導入し、基板温度を６
００°Ｃとして平均粒径１〇−の三珪化五モリブデンの
粉末を溶射して１〇−厚さの珪化物皮膜を形成した。そ
の後、燐酸系張力皮膜溶液を塗布し、８５０°Ｃで６０
秒間の焼付は処理を行った。こうして得られた製品の磁
気時を低下させることができ、その工業的効果は甚大で
ある。After mirror finishing and 3JnB chrome plating, the steel plate was introduced into a low-pressure plasma spraying device and the substrate temperature was raised to 6.
A powder of pentamolybdenum trisilicide having an average particle size of 10°C was thermally sprayed at 00°C to form a silicide film with a thickness of 10°C. After that, a phosphoric acid-based tension coating solution was applied and
The second baking process was performed. The magnetic time of the product thus obtained can be lowered, and its industrial effects are enormous.
【図面の簡単な説明】
第１図は溶射すべき珪化物粉末の粒径と形成される珪化
物皮膜の厚さの関係を示す図、第２図は溶射時の基板の
温度と溶射後の溶射皮膜の密着性の関係を示す図である
。
性を第２表に示す。
第２表
本発明の低圧プラズマ溶射による鋼板表面における珪化
物皮膜形成後、張力皮膜形成処理を施すとさらに鉄損が
向上（鉄損値が低下）していることがわかる。
（発明の効果）[Brief explanation of the drawings] Figure 1 shows the relationship between the particle size of the silicide powder to be thermally sprayed and the thickness of the silicide film formed, and Figure 2 shows the relationship between the temperature of the substrate during thermal spraying and the thickness of the silicide film after thermal spraying. It is a figure showing the relationship of adhesion of a thermal spray coating. The properties are shown in Table 2. Table 2 It can be seen that the iron loss further improves (the iron loss value decreases) when a tension film formation treatment is performed after the silicide film is formed on the surface of the steel plate by the low-pressure plasma spraying of the present invention. (Effect of the invention)
Claims (2)
表面に金属メッキを施した後、低圧プラズマ溶射法にて
珪化物皮膜を形成せしめることを特徴とする低鉄損一方
向性珪素鋼板の製造方法。(1) Low core loss unidirectionality characterized by applying metal plating to the smoothed base steel surface of the unidirectional silicon steel plate after finish annealing, and then forming a silicide film by low pressure plasma spraying. Method of manufacturing silicon steel plate.
表面に金属メッキを施した後、低圧プラズマ溶射法にて
珪化物皮膜を形成せしめ、さらに張力付与膜を塗布焼付
けすることを特徴とする低鉄損一方向性珪素鋼板の製造
方法。(2) After applying metal plating to the smoothed base steel surface of the unidirectional silicon steel sheet after final annealing, a silicide film is formed using a low-pressure plasma spraying method, and a tension imparting film is further applied and baked. A method for manufacturing a unidirectional silicon steel sheet with a characteristic low core loss.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2096885A JPH03294468A (en) | 1990-04-12 | 1990-04-12 | Production of grain-oriented silicon steel sheet having small iron loss |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2096885A JPH03294468A (en) | 1990-04-12 | 1990-04-12 | Production of grain-oriented silicon steel sheet having small iron loss |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03294468A true JPH03294468A (en) | 1991-12-25 |
Family
ID=14176858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2096885A Pending JPH03294468A (en) | 1990-04-12 | 1990-04-12 | Production of grain-oriented silicon steel sheet having small iron loss |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03294468A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913488A2 (en) * | 1997-10-28 | 1999-05-06 | Kawasaki Steel Corporation | Grain oriented electrical steel sheet and method |
| JP2006135061A (en) * | 2004-11-05 | 2006-05-25 | Nippon Steel Corp | Electromagnetic steel plate having small relative permeability in board thickness direction |
| JP2012526196A (en) * | 2009-05-08 | 2012-10-25 | ズルツァー・メットコ・アクチェンゲゼルシャフト | Method for coating a substrate and substrate having a coating |
-
1990
- 1990-04-12 JP JP2096885A patent/JPH03294468A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0913488A2 (en) * | 1997-10-28 | 1999-05-06 | Kawasaki Steel Corporation | Grain oriented electrical steel sheet and method |
| EP0913488A3 (en) * | 1997-10-28 | 2003-01-29 | Kawasaki Steel Corporation | Grain oriented electrical steel sheet and method |
| JP2006135061A (en) * | 2004-11-05 | 2006-05-25 | Nippon Steel Corp | Electromagnetic steel plate having small relative permeability in board thickness direction |
| JP2012526196A (en) * | 2009-05-08 | 2012-10-25 | ズルツァー・メットコ・アクチェンゲゼルシャフト | Method for coating a substrate and substrate having a coating |
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