JP5858052B2 - コーティング付き方向性電磁鋼板およびその製造方法 - Google Patents
コーティング付き方向性電磁鋼板およびその製造方法 Download PDFInfo
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- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000576 coating method Methods 0.000 claims description 76
- 239000011248 coating agent Substances 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 30
- 229910019142 PO4 Inorganic materials 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 28
- 239000010452 phosphate Substances 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 239000008119 colloidal silica Substances 0.000 claims description 10
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 9
- -1 chromic acid compound Chemical class 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 238000005097 cold rolling Methods 0.000 claims description 4
- 238000005098 hot rolling Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000005365 phosphate glass Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229910052839 forsterite Inorganic materials 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910001347 Stellite Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Description
そのため、リン酸系ガラスコーティングは、特に一般的に用いられる張力コーティングであり、様々な技術が提案されている(例えば、特許文献3〜5を参照)。
(1)方向性電磁鋼板と、上記方向性電磁鋼板の表面に形成され、P,Si,CrおよびOの元素、ならびに、Mg,Al,Ni,Co,Mn,Zn,Fe,CaおよびBaからなる群から選ばれる少なくとも1種の元素を含有し、5質量%以上がリン酸塩の結晶相であるコーティングと、を備えるコーティング付き方向性電磁鋼板。
(i)800≦T<860,T≧1010−399R,0.1≦R≦0.5
(ii)860≦T≦1000,T≧985−399R,0.1≦R≦0.5
まず、本発明に至った経緯を説明する。
本発明者らは、第一リン酸Mg、コロイダルシリカ、および無水クロム酸を様々な組成比で含有するコーティング処理液を調製し、これをフォルステライト被膜を有する方向性電磁鋼板に塗布し、焼き付け処理における鋼板温度での均熱時間20秒で焼付け処理を行い、形成されるコーティングが方向性電磁鋼板に与える引張応力、およびその他の特性を測定した。なお、引張応力の測定は、片面のコーティングを苛性ソーダで除去した際の方向性電磁鋼板の反り量を換算することにより行なった。
次に、本発明のコーティング付き方向性電磁鋼板の製造方法(以下、単に「本発明の製造方法」ともいう)について説明する。
以下、各工程を詳細に説明する。
準備工程によって準備される方向性電磁鋼板の成分組成は特に限定されず、従来公知のものを用いることができるが、鉄損の低減をより優れたものにするためには、二次再結晶粒径が小さいものを用いることが好ましい。
コーティング工程は、上述した準備工程で準備された方向性電磁鋼板の表面にコーティング処理液を塗布した後に焼付け処理を行うことによりコーティング付き方向性電磁鋼板を得る工程である。
これらのうち、結晶化しやすい第一リン酸Mgを用いることが、より優れた引張応力が得られるという理由から好ましい。
(ii)860≦T≦1000,T≧985−399R,0.1≦R≦0.5
(iii)860≦T≦1000,T≧1010−399R,0.1≦R≦0.5
鋼板温度Tの範囲は、方向性電磁鋼板の塑性伸びを抑制するという観点からは、800〜900℃が好ましい。
質量比Rは、焼付け処理の低温化という観点からは高い方が好ましく、具体的には0.2以上が好ましく、0.3以上がより好ましい。
次に、本発明のコーティング付き方向性電磁鋼板について説明する。
本発明のコーティング付き方向性電磁鋼板は、本発明の製造方法によって得られるものであり、概略的には、方向性電磁鋼板と、この方向性電磁鋼板の表面に形成されたコーティング(以下、「本発明のコーティング」ともいう)とを備える。
次いで、830℃、1分間の脱炭焼鈍(一次再結晶焼鈍)後、MgOを主成分とする焼鈍分離剤を表面に塗布した後、1200℃、5時間の最終仕上げ焼鈍を施すことにより、フォルステライト被膜を有する方向性電磁鋼板を得た。
このとき、サンプルごとに、一次再結晶焼鈍における500〜700℃の昇温過程の昇温速度を変化させた。昇温速度(単位:℃/秒)を下記第1表に示す。
このとき、一次再結晶焼鈍における500〜700℃の昇温速度が80または250℃/秒であるサンプル(No.22および23)は、当該昇温速度が20℃/秒であるサンプルよりも、鉄損の低減により優れることが分かった。
図1においては、測定された引張応力が11MPa未満であった場合には、引張応力が低く鉄損の低減に劣るものとして「×」をプロットし、11〜13MPaであった場合には、引張応力が高く鉄損の低減に優れるものとして「○」をプロットし、13MPa超であった場合には、引張応力がより高く鉄損の低減に非常に優れるものとして「◎」をプロットした。
とりわけ、上記条件(iii)を満たす範囲のプロットは全て「◎」であり、引張応力がより高く鉄損の低減に非常に優れることが分かった。
Claims (2)
- 方向性電磁鋼板を準備する工程と、
Mg,Al,Ni,Co,Mn,Zn,Fe,CaおよびBaからなる群から選ばれる少なくとも1種の元素を含む第一リン酸塩と、コロイダルシリカと、無水クロム酸、クロム酸塩および重クロム酸塩からなる群から選ばれる少なくとも1種のクロム酸化合物とを含有するコーティング処理液を、前記方向性電磁鋼板の表面に塗布した後に焼付け処理を行うことによりコーティング付き方向性電磁鋼板を得る工程と、
を備え、
前記焼付け処理における鋼板温度(単位:℃)をTとし、前記コーティング処理液が含有する前記クロム酸化合物(Cr2O3換算)と前記第一リン酸塩(P2O5換算)との質量比(Cr2O3/P2O5)をRとした場合に、下記条件(i)または(ii)を満たす、
コーティング付き方向性電磁鋼板の製造方法。
(i)800≦T<860,T≧1010−399R,0.3≦R≦0.5
(ii)860≦T≦1000,T≧985−399R,0.3≦R≦0.5 - 前記方向性電磁鋼板を準備する工程が、方向性電磁鋼板用スラブを、熱間圧延し、熱延板焼鈍した後、1回または中間焼鈍を挟む2回以上の冷間圧延をし、次いで、一次再結晶焼鈍した後、焼鈍分離剤を塗布してから最終仕上げ焼鈍を施すことにより、前記方向性電磁鋼板を得る工程であって、
前記一次再結晶焼鈍における500〜700℃の昇温過程の昇温速度が、50〜300℃/秒である、
請求項1に記載のコーティング付き方向性電磁鋼板の製造方法。
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