JP7226662B1 - 無方向性電磁鋼板およびその製造方法 - Google Patents
無方向性電磁鋼板およびその製造方法 Download PDFInfo
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- JP7226662B1 JP7226662B1 JP2022548549A JP2022548549A JP7226662B1 JP 7226662 B1 JP7226662 B1 JP 7226662B1 JP 2022548549 A JP2022548549 A JP 2022548549A JP 2022548549 A JP2022548549 A JP 2022548549A JP 7226662 B1 JP7226662 B1 JP 7226662B1
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- steel sheet
- oriented electrical
- electrical steel
- resins
- phosphate
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- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000576 coating method Methods 0.000 claims abstract description 105
- 239000011248 coating agent Substances 0.000 claims abstract description 97
- 239000002131 composite material Substances 0.000 claims abstract description 67
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 61
- 239000010452 phosphate Substances 0.000 claims abstract description 61
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 46
- 239000010959 steel Substances 0.000 claims abstract description 46
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- 229920005989 resin Polymers 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000004736 wide-angle X-ray diffraction Methods 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052782 aluminium Inorganic materials 0.000 claims description 6
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- 229920000647 polyepoxide Polymers 0.000 claims description 6
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- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 abstract description 7
- 229910000976 Electrical steel Inorganic materials 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 60
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 41
- 230000000903 blocking effect Effects 0.000 description 25
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- 235000011007 phosphoric acid Nutrition 0.000 description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 20
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- 230000007797 corrosion Effects 0.000 description 9
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- 239000000126 substance Substances 0.000 description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
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- 230000000593 degrading effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 238000010030 laminating Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1283—Application of a separating or insulating coating
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
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- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Electromagnetism (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
本実施形態に係る無方向性電磁鋼板は、母材鋼板と、母材鋼板の表面に形成された複合皮膜とを備える。一般的に、無方向性電磁鋼板の絶縁皮膜を大別すると、全有機皮膜(皮膜全てが有機物で構成されたもの)、無機皮膜(皮膜全てが無機物で構成されたもの)、および複合皮膜(皮膜が有機物および無機物の組み合わせで構成されたものであり、半有機皮膜とも称される)の3種類がある。本実施形態に係る無方向性電磁鋼板の絶縁皮膜は、複合皮膜である。
本実施形態に係る無方向性電磁鋼板において、複合皮膜に無機物としてリン酸塩を含有する。本発明においては、Zn成分を溶出させることで耐食性を改善させるという技術思想に基づいているため、Zn含有リン酸塩を必須とする。すなわち、本発明において、複合皮膜は、Zn含有リン酸塩と有機樹脂とを含む。
本実施形態に係る無方向性電磁鋼板の母材鋼板は特に限定されない。本実施形態に係る無方向性電磁鋼板の課題の一つである耐食性向上は、絶縁皮膜中にZnを含有することによって達成されるからである。母材鋼板は、無方向性電磁鋼板の母材鋼板として用いられる通常の鋼板から適宜選択することができる。
本実施形態に係る無方向性電磁鋼板は、塗布液を母材鋼板の表面に塗布する工程と、その後、塗布液を焼き付けることにより母材鋼板上に複合皮膜を形成する工程とを備える製造方法により製造することができる。
母材鋼板の表面に塗布する塗布液は、リン酸塩水溶液と有機樹脂水分散液とδ-Al2O3とを含む。また、リン酸塩水溶液における金属成分にはZn成分を含有させる。リン酸塩として存在するZn以外の金属成分としては、原料価格および入手し易さ等を考えると、Al、Mg、およびCa等が挙げられるが、これに限定されない。
上述のように、調製した塗布液を焼き付ける際には、雰囲気の制御が重要となる。本発明者らが行った研究の結果、δ-Al2O3によってフリーリン酸を固定できていたとしても、焼き付け後の皮膜の表面性状が劣化している場合には、ブロッキング現象が生じてしまう場合があることが分かった。そして、皮膜の表面性状に焼き付け雰囲気中の空気比が大きく影響を与えていることを見出した。
m=A/A0
複合皮膜を形成する前であって、焼鈍済みの板厚0.5mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。この母材鋼板に対し、リン酸Alおよびリン酸Znの混合物でZnモル比率を20%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%のアクリル-スチレン樹脂水分散液40gと、粒径15nmのδ-Al2O3粉末2.0gとの混合液を塗布した。そして、直火加熱式バーナーにおいて、最高到達温度を340℃として、種々の空気比で複合皮膜を形成した。
・垂直剥離力が500g以下の場合 : A
・垂直剥離力が500g超1000g以下の場合 : B
・垂直剥離力が1000g超1500g以下の場合: C
・垂直剥離力が1500g超の場合 : D
複合皮膜を形成する前であって、焼鈍済みの板厚0.5mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。この母材鋼板に対し、リン酸Alおよびリン酸Znの混合物でZnモル比率を20%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%のアクリル-スチレン樹脂水分散液20gと、表2に示す添加量の粒径100nmのα-Al2O3粉末または粒径10nmのδ-Al2O3粉末との混合液を塗布した。なお、表2に示す試験No.2-1については、いずれのAl2O3粉末も添加しなかった。そして、直火加熱式バーナーにおいて、最高到達温度を340℃、空気比を1.5として複合皮膜を形成した。
複合皮膜を形成する前であって、焼鈍済みの板厚0.5mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。この母材鋼板に対し、リン酸Mgおよびリン酸Znの混合物でZnモル比率を40%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%のアクリル-スチレン樹脂水分散液20gと、粒径20nmのδ-Al2O3粉末30gとの混合液を塗布した。そして、直火加熱式バーナーにおいて、最高到達温度を340℃、空気比を1.5として複合皮膜を形成した。
複合皮膜を形成する前であって、焼鈍済みの板厚0.35mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。これらの母材鋼板に対し、リン酸Caおよびリン酸Znの混合物でZnモル比率を30%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%のアクリル-スチレン樹脂水分散液10gと、粒径40nmのδ-Al2O3粉末20gとの混合液を塗布した。そして、直火加熱式バーナーにおいて、最高到達温度を340℃、空気比を1.2として複合皮膜を形成した。
複合皮膜を形成する前であって、焼鈍済みの板厚0.5mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。これらの母材鋼板に対し、リン酸Alおよびリン酸Znの混合物でZnモル比率を40%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%で表5に示す種々の有機樹脂水分散液30gと、粒径15nmのδ-Al2O3粉末10gとの混合液を塗布した。そして、直火加熱式バーナーにおいて、最高到達温度を340℃、空気比を1.5として複合皮膜を形成した。
複合皮膜を形成する前であって、焼鈍済みの板厚0.5mmの無方向性電磁鋼板(すなわち母材鋼板)を用意した。この母材鋼板に対し、リン酸Alおよびリン酸Znの混合物でZnモル比率を20%に調整した、固形分濃度が50%のリン酸塩水溶液200g(リン酸塩100g)と、濃度が40%のアクリル-スチレン樹脂水分散液20gと、粒径30nmのδ-Al2O3粉末20gとの混合液を塗布した。そして、直火加熱式バーナーにおいて、空気比を1.5として、表6に示す種々の最高到達温度で複合皮膜を形成した。
Claims (7)
- 母材鋼板と、
前記母材鋼板の表面に形成された、Zn含有リン酸塩と有機樹脂との複合皮膜と、
を備える無方向性電磁鋼板であって、
前記複合皮膜を広角X線回折法で測定した時に、ICDD番号01-074-3256に帰属する回折線を示す結晶性リン酸アルミニウムを含む、
無方向性電磁鋼板。 - 複数の前記無方向性電磁鋼板を接触面積9cm2で積層し、面圧40kgf/cm2で加圧し、温度50℃、湿度90%の雰囲気中に56日間保持した後、室温にて測定される垂直剥離力が1000g以下である、
請求項1に記載の無方向性電磁鋼板。 - 前記複合皮膜が、さらにMgおよびCaからなる群から選択される一種以上を含む、
請求項1または請求項2に記載の無方向性電磁鋼板。 - 前記有機樹脂が、アクリル樹脂、スチレン樹脂、アクリル-スチレン樹脂、エポキシ樹脂、ポリエステル樹脂、フェノール樹脂、およびウレタン樹脂からなる群から選択される一種以上を含む、
請求項1から請求項3までのいずれかに記載の無方向性電磁鋼板。 - Zn含有リン酸塩と有機樹脂とδ-Al2O3とを含む塗布液を、母材鋼板の表面に塗布する工程と、
前記塗布液を空気比1.8以下の雰囲気中で、最大到達温度が250~450℃の範囲で焼き付け、複合皮膜を形成する工程と、を備える、
無方向性電磁鋼板の製造方法。 - 前記塗布液が、さらに、Al、Mg、およびCaからなる群から選択される一種以上を含有する、
請求項5に記載の無方向性電磁鋼板の製造方法。 - 前記有機樹脂が、アクリル樹脂、スチレン樹脂、アクリル-スチレン樹脂、エポキシ樹脂、ポリエステル樹脂、フェノール樹脂、およびウレタン樹脂からなる群から選択される一種以上である、
請求項5または請求項6に記載の無方向性電磁鋼板の製造方法。
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