JP5862582B2 - Method for producing grain-oriented electrical steel sheet, grain-oriented electrical steel sheet and surface glass coating for grain-oriented electrical steel sheet - Google Patents
Method for producing grain-oriented electrical steel sheet, grain-oriented electrical steel sheet and surface glass coating for grain-oriented electrical steel sheet Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims description 45
- 239000011248 coating agent Substances 0.000 title claims description 44
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims description 39
- 239000011521 glass Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 238000000137 annealing Methods 0.000 claims description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 229910000831 Steel Inorganic materials 0.000 claims description 55
- 239000010959 steel Substances 0.000 claims description 55
- 238000001953 recrystallisation Methods 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 238000005121 nitriding Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- -1 phosphate compound Chemical class 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 229910052839 forsterite Inorganic materials 0.000 claims description 16
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 229910052742 iron Inorganic materials 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 15
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 15
- 229910052581 Si3N4 Inorganic materials 0.000 description 14
- 239000011651 chromium Substances 0.000 description 14
- 238000005097 cold rolling Methods 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 238000005261 decarburization Methods 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005098 hot rolling Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000976 Electrical steel Inorganic materials 0.000 description 3
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000005365 phosphate glass Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、優れた磁気特性を有する方向性電磁鋼板を安価に得ることができる磁気特性に優れた方向性電磁鋼板の製造方法およびその製造方法を用いた方向性電磁鋼板並びに方向性電磁鋼板用表面ガラスコーティングに関するものである。 The present invention relates to a method for producing a grain-oriented electrical steel sheet having excellent magnetic properties, capable of obtaining a grain-oriented electrical steel sheet having excellent magnetic properties, and a grain-oriented electrical steel sheet and grain-oriented electrical steel sheet using the production method. It relates to surface glass coating.
方向性電磁鋼板は、変圧器や発電機の鉄心材料として用いられる軟磁性材料で、鉄の磁化容易軸である＜001＞方位が鋼板の圧延方向に高度に揃った結晶組織を有するものである。このような集合組織は、方向性電磁鋼板の製造工程中、二次再結晶焼鈍の際にいわゆるゴス（Goss）方位と称される{110}<001>方位の結晶粒を優先的に巨大成長させる、二次再結晶を通じて形成される。 A grain-oriented electrical steel sheet is a soft magnetic material used as a core material for transformers and generators, and has a crystal structure in which the <001> orientation, which is the easy axis of iron, is highly aligned in the rolling direction of the steel sheet. . Such a texture preferentially grows grains of the {110} <001> orientation called the Goss orientation during secondary recrystallization annealing during the production process of grain-oriented electrical steel sheets. Formed through secondary recrystallization.
従来、このような方向性電磁鋼板は、4.5mass％以下程度のSiと、MnS，MnSeおよびAlNなどのインヒビター成分を含有するスラブを、1300℃以上に加熱し、インヒビター成分を一旦固溶させたのち、熱間圧延し、必要に応じて熱延板焼鈍を施して、１回または中間焼鈍を挟む２回以上の冷間圧延によって最終板厚とし、ついで湿潤水素雰囲気中で一次再結晶焼純を施して、一次再結晶および脱炭を行い、ついでマグネシア（MgO）を主剤とする焼鈍分離剤を塗布してから、二次再結晶およびインヒビター成分の純化のために、1200℃で５ｈ程度の最終仕上焼鈍を行うことによって製造されてきた（例えば、特許文献１、特許文献２および特許文献３）。 Conventionally, such a grain-oriented electrical steel sheet is heated to 1300 ° C or higher by heating a slab containing about 4.5 mass% or less of Si and an inhibitor component such as MnS, MnSe, and AlN to once dissolve the inhibitor component. After that, it is hot-rolled and subjected to hot-rolled sheet annealing as necessary, to obtain the final sheet thickness by one or more cold rollings sandwiching intermediate annealing, followed by primary recrystallization annealing in a wet hydrogen atmosphere After performing primary recrystallization and decarburization, and then applying an annealing separator mainly composed of magnesia (MgO), the secondary recrystallization and the inhibitor component are purified at 1200 ° C. for about 5 hours. It has been manufactured by performing final finish annealing (for example, Patent Document 1, Patent Document 2, and Patent Document 3).
上述したとおり、従来の方向性電磁鋼板の製造に際しては、MnS，MnSe，AlNなどの析出物（インヒビター成分）をスラブ段階で含有させて、1300℃を超える高温のスラブ加熱をすることにより、これらのインヒビター成分を一旦固溶させ、後工程で微細析出させることによって二次再結晶を発現させるという工程が採用されてきた。 As described above, when producing conventional grain-oriented electrical steel sheets, precipitates (inhibitor components) such as MnS, MnSe, and AlN are included in the slab stage, and these are heated at a high temperature exceeding 1300 ° C. The step of causing secondary recrystallization by once dissolving the inhibitor component of this compound and then precipitating it finely in a subsequent step has been adopted.
このように、従来の方向性電磁鋼板の製造工程では、1300℃を超える高温でのスラブ加熱が必要であったため、その製造コストは極めて高いものにならざるを得ず、近年の製造コスト低減の要求に応えることができないというところに問題を残していた。 As described above, in the manufacturing process of conventional grain-oriented electrical steel sheets, slab heating at a high temperature exceeding 1300 ° C. is necessary, so the manufacturing cost has to be extremely high, and in recent years the manufacturing cost has been reduced. He left a problem where he was unable to meet the demand.
こうした問題を解決するために、例えば、特許文献４では、酸可溶性Al（sol.Al）を0.010〜0.060％含有させ、スラブ加熱を低温に抑えて脱炭焼鈍工程で適正な窒化雰囲気を用いて窒化を行なうことにより、二次再結晶時に（Al，Si）Nを析出させインヒビターとして用いる方法が提案されている。（Al，Si）Nは鋼中に微細分散することで有効なインヒビターとして機能するが、Alの含有量によってインヒビター強度が決まるために、製鋼でのAl的中精度が不十分な場合は、十分な粒成長抑制力が得られない場合があった。このような途中工程で窒化処理を行ない、（Al，Si）NあるいはAlNをインヒビターとして利用する方法が数多く提案されているが、最近では、スラブ加熱温度が1300℃を超える製造方法等が開示されている。 In order to solve such a problem, for example, in Patent Document 4, 0.010 to 0.060% of acid-soluble Al (sol. Al) is contained, slab heating is suppressed to a low temperature, and an appropriate nitriding atmosphere is used in the decarburization annealing process. A method has been proposed in which (Al, Si) N is precipitated during secondary recrystallization by nitriding and used as an inhibitor. (Al, Si) N functions as an effective inhibitor by being finely dispersed in the steel, but since the inhibitor strength is determined by the Al content, it is sufficient if the accuracy of Al in steelmaking is insufficient. In some cases, it was not possible to obtain a sufficient grain growth inhibiting force. Numerous methods have been proposed in which nitriding is performed in the middle of the process and (Al, Si) N or AlN is used as an inhibitor. Recently, however, a manufacturing method in which the slab heating temperature exceeds 1300 ° C. has been disclosed. ing.
一方、そもそもスラブにインヒビター成分を含有させずに二次再結晶を発現させる技術については、特許文献５に、インヒビター成分を含有させなくとも二次再結晶ができる技術（インヒビターレス法）が開示されている。
ここに、インヒビターレス法は、より高純度化した鋼を利用し、テクスチャー（集合組織の制御）によって二次再結晶を発現させる技術である。しかしながら、インヒビターレス法では、高温のスラブ加熱が不要であって、低コストでの方向性電磁鋼板の製造が可能であるものの、インヒビターを有しないが故に、製造工程中での温度ばらつきなどの影響を受けて、製品での磁気特性にバラつきが生じやすいといった不利があった。
On the other hand, as a technique for causing secondary recrystallization without including an inhibitor component in the slab, Patent Document 5 discloses a technique (inhibitorless method) capable of performing secondary recrystallization without containing an inhibitor component. ing.
Here, the inhibitorless method is a technique in which secondary recrystallization is manifested by texture (control of texture) using higher-purity steel. However, the inhibitorless method does not require high-temperature slab heating and enables production of grain-oriented electrical steel sheets at a low cost. As a result, there is a disadvantage that the magnetic characteristics of the product are likely to vary.
また、集合組織の制御は、磁気特性に対して重要な要素であるため、集合組織制御を行う温間圧延などには、多くの条件が提案されている。こうした集合組織制御が十分に行なえない場合は、インヒビターを用いる技術に比べると、二次再結晶後のゴス方位（{110}<001>）への集積度が低く、磁束密度も低くなる。 In addition, since texture control is an important factor for magnetic properties, many conditions have been proposed for warm rolling and the like in which texture control is performed. When this texture control cannot be performed sufficiently, the degree of integration in the Goth orientation ({110} <001>) after secondary recrystallization is low and the magnetic flux density is low as compared with the technique using an inhibitor.
上述したとおり、これまで提案されてきた方向性電磁鋼板の製造方法では、良好な磁気特性を安定的に実現することが難しい場合が多かった。
これに対し、発明者らは、Alを100ppm未満に抑制したインヒビターレス成分に準じた成分を用いて、高温スラブ加熱を回避しつつ、窒素増量を適用することで、AlNではなく窒化珪素を析出させ、この窒化珪素を正常粒成長の抑制力として機能させることで、磁気特性のバラつきを大幅に低減し、工業的に安定して良好な特性を有する方向性電磁鋼板の製造方法に想到した。
As described above, it has often been difficult to stably achieve good magnetic properties in the method of manufacturing grain-oriented electrical steel sheets that has been proposed so far.
On the other hand, the inventors deposited silicon nitride instead of AlN by applying nitrogen augmentation while avoiding high-temperature slab heating using a component according to the inhibitorless component in which Al was suppressed to less than 100 ppm. Thus, by making this silicon nitride function as a suppressive force for normal grain growth, the inventors have come up with a method for producing grain-oriented electrical steel sheets that have significantly reduced variations in magnetic properties and have industrially stable and good properties.
ここで、一般に、方向性電磁鋼板においては、絶縁性、加工性および防錆性等を付与するため、表面にリン酸ガラス質の被膜をもうける。
この被膜は高温で形成され、しかも低い熱膨張率を持つことから室温まで下がったときの鋼板と被膜との熱膨張率の差異によって鋼板に張力を付与することができ、この張力によって鋼板の鉄損を低減させる効果がある。この時、高い張力を鋼板に付与することで、鋼板の鉄損低減効果も一段と向上するので、できるだけ高い張力を鋼板に付与することが望まれている。
Here, in general, in a grain-oriented electrical steel sheet, a phosphate glassy coating is provided on the surface in order to provide insulation, workability, rust prevention, and the like.
Since this coating is formed at a high temperature and has a low coefficient of thermal expansion, tension can be imparted to the steel sheet due to the difference in thermal expansion coefficient between the steel sheet and the coating when lowered to room temperature. There is an effect of reducing the loss. At this time, by applying a high tension to the steel sheet, the effect of reducing the iron loss of the steel sheet is further improved. Therefore, it is desired to apply as high a tension as possible to the steel sheet.
この要望を満たすために、従来から種々の被膜が提案されている。例えば、特許文献６には、リン酸マグネシウム、コロイド状シリカおよび無水クロム酸を主体とする被膜が、また特許文献７には、リン酸アルミニウム、コロイド状シリカおよび無水クロム酸を主体とする被膜がそれぞれ提案されている。 In order to satisfy this demand, various coatings have been proposed conventionally. For example, Patent Document 6 includes a film mainly composed of magnesium phosphate, colloidal silica and chromic anhydride, and Patent Document 7 includes a film mainly composed of aluminum phosphate, colloidal silica and chromic anhydride. Each has been proposed.
また、近年の環境保全への関心の高まりにより、クロムや鉛等の有害物質を含まない製品に対する要望が高まっている。
この要望に対しては、特許文献８でコロイド状シリカとリン酸アルミニウム、ホウ酸および硫酸塩からなる処理液を用いた被膜形成方法が提案されている。
また、特許文献９にはクロム化合物の代わりにホウ酸化合物を添加する方法が、特許文献１０には酸化物コロイドを添加する方法が、さらには特許文献１１に金属有機酸塩を添加する方法が、それぞれ開示されている。
In addition, due to the recent increase in interest in environmental conservation, there is an increasing demand for products that do not contain harmful substances such as chromium and lead.
In response to this demand, Patent Document 8 proposes a film forming method using a treatment liquid composed of colloidal silica and aluminum phosphate, boric acid and sulfate.
Patent Document 9 includes a method of adding a boric acid compound instead of a chromium compound, Patent Document 10 includes a method of adding an oxide colloid, and Patent Document 11 further includes a method of adding a metal organic acid salt. , Respectively.
しかしながら、鋼板を窒化し、窒化珪素を析出させることで正常粒成長の抑制力として使用する方向性電磁鋼板にこれらの技術を適用した場合、ガラスコーティング後の製品の状態における鋼板中の窒素量が過剰となって、需要家への出荷時点で鉄損の悪化をまねいたり、あるいは需要家でのひずみとり焼鈍時に鋼板中へ窒化物が析出して特性の劣化を招いたり、という新たな問題が発生した。 However, when these technologies are applied to grain-oriented electrical steel sheets that are used as a suppressive force for normal grain growth by nitriding steel sheets and precipitating silicon nitride, the amount of nitrogen in the steel sheets in the product state after glass coating is reduced. There is a new problem that it becomes excessive and causes deterioration of iron loss at the time of shipment to the customer, or nitride precipitates in the steel sheet during strain relief annealing at the customer and causes deterioration of characteristics. Occurred.
本発明は、上記の現状に鑑み開発されたもので、窒化珪素を形成する目的で二次再結晶前の鋼板に窒素を加えた方向性電磁鋼板が、窒素を鋼中へ効率的に拡散させ、窒化珪素を粒界に析出させることで、良好な磁気特性を有する方向性電磁鋼板の製造方法を、その製造方法を用いた方向性電磁鋼板および方向性電磁鋼板用表面ガラスコーティングと共に提供することを目的とする。 The present invention has been developed in view of the above situation, and a grain-oriented electrical steel sheet in which nitrogen is added to a steel sheet before secondary recrystallization for the purpose of forming silicon nitride effectively diffuses nitrogen into the steel. And providing a method for producing a grain-oriented electrical steel sheet having good magnetic properties by precipitating silicon nitride at grain boundaries together with a grain-oriented electrical steel sheet using the production method and a surface glass coating for the grain-oriented electrical steel sheet. With the goal.
窒化珪素を用いる本発明では、仕上焼鈍（二次再結晶焼鈍）後にも従来法と比べて多量の窒素が窒化物、酸窒化物その他の形態でフォルステライト被膜中に残留する。例えば、窒化を行わない場合にはフォルステライト中に質量％で１％未満であるものが、本発明では１質量％以上となってしまうのである。 In the present invention using silicon nitride, even after finish annealing (secondary recrystallization annealing), a larger amount of nitrogen remains in the forsterite film in the form of nitride, oxynitride or the like than in the conventional method. For example, in the case where nitriding is not performed, forsterite that is less than 1% by mass is 1% by mass or more in the present invention.
このように、フォルステライト中に過剰に蓄積された窒素は、仕上焼鈍後に引続き行われるガラスコーティング形成や、平坦化焼鈍時、さらには需要家での歪取焼鈍などの800℃以上の焼鈍にさらされると、一部が鋼中へ戻ってしまい、結果的に鋼中窒素濃度が高くなってしまう。 In this way, the excessively accumulated nitrogen in the forsterite is exposed to annealing at 800 ° C or higher during glass coating formation, flattening annealing, and even stress relief annealing at the customer after finishing annealing. As a result, a part of it returns to the steel, resulting in an increase in the nitrogen concentration in the steel.
そこで、発明者らは、８００℃以上の高温にさらされても、フォルステライト被膜中に固定された窒素が、再び鋼中に戻ることを防止する技術を鋭意検討した。その結果、ガラスコーティング中にガラス中のＰ（リン）量にあわせて適正量の窒化物形成能を持つ元素を含有させることで、フォルステライト被膜中へ窒素を固定し続けることができる方法を見出し、本発明を完成させた。 Therefore, the inventors diligently studied a technique for preventing nitrogen fixed in the forsterite film from returning to the steel again even when exposed to a high temperature of 800 ° C. or higher. As a result, we found a method that can continue to fix nitrogen in the forsterite film by including an appropriate amount of nitride-forming elements in the glass coating in accordance with the amount of P (phosphorus) in the glass. The present invention has been completed.
本発明の要旨構成は次のとおりである。
１．質量％で、Ｃ：0.08％以下、Si：2.0〜4.5％およびMn：0.5％以下を含有すると共に、Ｓ、SeおよびＯをそれぞれ50質量ppm未満、sol.Alを100質量ppm未満に抑制し、さらにＮを〔酸可溶性Al（sol.Al）質量ppm／26.98〕×14.00≦Ｎ≦80質量ppmの範囲に制御し、残部はFeおよび不可避的不純物の組成になる鋼スラブを、再加熱することなくあるいは再加熱後、熱間圧延を施して熱延板としたのち、焼鈍および圧延によって最終板厚の冷間圧延板とし、二次再結晶焼鈍前までに窒素増量が50質量ppm以上1000質量ppm以下となる窒化処理を施した後、焼鈍分離剤を塗布し、二次再結晶焼鈍の昇温過程において、300〜800℃間の滞留時間を５時間以上150時間以下とし、さらに、二次再結晶焼鈍後に焼鈍分離剤を除去してガラスコーティング液を塗布、焼付けることで、リン酸ガラスを主体とするガラスコーティングを鋼板表面に形成する一連の方向性電磁鋼板の製造において、
上記焼鈍分離剤が、MgOを50％以上含有し、かつＭをTi、Mn、Si、Cr、AlおよびＢのいずれかとした時のＭの酸化物を、焼鈍分離剤100質量部に対し、ＭＯｘ換算で５質量部以上20質量部以下含有し、さらに
上記ガラスコーティング液が、リン酸塩化合物と、ＡをAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのいずれかとしたＡの酸化物を１種または２種以上とを含み、かつ該酸化物の金属成分Ａの合計：Ｚ（mol）と、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）が0.08≦Z/P≦0.8の関係を満足することを特徴とする方向性電磁鋼板の製造方法。
The gist of the present invention is as follows.
1. In addition to containing C: 0.08% or less, Si: 2.0 to 4.5%, and Mn: 0.5% or less, S, Se, and O are each suppressed to less than 50 ppm by mass, and sol.Al is suppressed to less than 100 ppm by mass. Further, N is controlled in the range of [acid-soluble Al (sol.Al) mass ppm / 26.98] × 14.00 ≦ N ≦ 80 mass ppm, and the remainder is reheated to a steel slab having a composition of Fe and inevitable impurities. Without re-heating or after re-heating, hot-rolled sheet is used to make a cold-rolled sheet with the final thickness by annealing and rolling. After performing nitriding treatment to a mass ppm or less, an annealing separator is applied, and in the temperature raising process of secondary recrystallization annealing, the residence time between 300-800 ° C. is set to 5 hours or more and 150 hours or less. After the next recrystallization annealing, the glass separator is removed by removing the annealing separator and baking. In the production of a series of grain-oriented electrical steel sheet to form a glass coating on the steel sheet surface mainly comprising,
The above-mentioned annealing separator contains 50% or more of MgO, and M is an oxide of M when M is any one of Ti, Mn, Si, Cr, Al and B with respect to 100 parts by mass of the annealing separator. 5 parts by weight or more and 20 parts by weight or less in terms of conversion, and the glass coating solution further comprises a phosphate compound and A as one of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn. 1 or 2 or more, and the total of metal components A of the oxide: molar ratio of Z (mol) and phosphorus in the phosphate compound : P (mol) (Z / P) satisfies the relationship of 0.08 ≦ Z / P ≦ 0.8. A method for producing a grain-oriented electrical steel sheet, wherein:
２．さらに、前記鋼スラブが、質量％で、
Ni：0.005〜1.50％、
Sn：0.01〜0.50％、
Sb：0.005〜0.50％、
Cu：0.01〜0.50％、
Cr：0.01〜1.50％、
Ｐ：0.0050〜0.50％、
Mo：0.01〜0.50％および
Nb：0.0005〜0.0100％
のうちから選んだ１種または２種以上を含有することを特徴とする前記１に記載の方向性電磁鋼板の製造方法。
2. Furthermore, the said steel slab is mass%,
Ni: 0.005-1.50%,
Sn: 0.01 to 0.50%,
Sb: 0.005-0.50%,
Cu: 0.01 to 0.50%,
Cr: 0.01 to 1.50%,
P: 0.0050 to 0.50%,
Mo: 0.01-0.50% and
Nb: 0.0005-0.0100%
The method for producing a grain-oriented electrical steel sheet according to 1 above, comprising one or more selected from among the above.
３．前記に記載の製造方法により得られる方向性電磁鋼板であって、ガラスコーティング直下のフォルステライトを主体とするセラミックス被膜中に窒素を１質量％以上10質量％以下含み、かつ該ガラスコーティング中に、リン酸塩化合物と、ＡがAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのいずれかであるＡの酸化物を１種または２種以上とを含み、さらに、上記酸化物の金属成分Ａの合計：Ｚ（mol）は、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）で0.08≦Z/P≦0.8の関係を満足することを特徴とする方向性電磁鋼板。 3. In the grain-oriented electrical steel sheet obtained by the production method described above, the ceramic film mainly composed of forsterite directly below the glass coating contains 1% by mass to 10% by mass of nitrogen, and the glass coating contains: A phosphate compound, and one or more oxides of A in which A is any one of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn, and The total of metal components A of the oxide: Z (mol) satisfies the relationship of 0.08 ≦ Z / P ≦ 0.8 in terms of molar ratio (Z / P) with phosphorus: P (mol) in the phosphate compound. A grain-oriented electrical steel sheet characterized by that.
４．前記１または２に記載の製造方法により得られる方向性電磁鋼板の表面コーティング用ガラスコーティングであって、該ガラスコーティング中に、リン酸塩化合物と、ＡがAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのうちいずれであるＡの酸化物を１種または２種以上とを含み、さらに、上記酸化物の金属成分Ａの合計：Ｚ（mol）は、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）で0.08≦Z/P≦0.8の関係を満足することを特徴とする方向性電磁鋼板用表面ガラスコーティング。 4). A glass coating for surface coating of a grain-oriented electrical steel sheet obtained by the production method according to 1 or 2, wherein a phosphate compound and A are Al, Ca, Ti, Nd, Mo, One or more oxides of A which is any of Cr, B, Ta, Cu and Mn, and the total of metal components A of the oxide: Z (mol) is the phosphoric acid A surface glass coating for grain-oriented electrical steel sheets characterized by satisfying a relationship of 0.08 ≦ Z / P ≦ 0.8 in a molar ratio (Z / P) with phosphorus: P (mol) in a salt compound .
本発明によれば、高温スラブ加熱を施さずとも、磁気特性のバラつきが大幅に低減され、工業的に安定して良好な特性を有する方向性電磁鋼板を得ることができる。 According to the present invention, even if high temperature slab heating is not performed, the magnetic property variation is greatly reduced, and a grain-oriented electrical steel sheet having industrially stable and good characteristics can be obtained.
以下、本発明を具体的に説明する。
まず、本発明において、鋼スラブの成分組成の限定理由について説明する。なお、以下に記載する「％」および「ppm」表示は特に断らない限り、それぞれ質量％および質量ppmを意味するものとする。
Ｃ:0.08％以下
Ｃは、一次再結晶集合組織を改善する上で有用な元素であるが、含有量が0.08％を超えると、かえって一次再結晶集合組織の劣化を招くので、本発明では0.08％以下に限定した。磁気特性の観点から望ましい添加量は、0.01〜0.06％の範囲である。なお、要求される磁気特性のレベルがさほど高くない場合には、一次再結晶焼鈍における脱炭を省略あるいは簡略化するために、Ｃを0.01％以下としてもよい。
Hereinafter, the present invention will be specifically described.
First, the reason for limiting the component composition of the steel slab in the present invention will be described. Unless otherwise specified, “%” and “ppm” described below mean mass% and mass ppm, respectively.
C: 0.08% or less C is an element useful for improving the primary recrystallization texture. However, if the content exceeds 0.08%, the primary recrystallization texture is deteriorated. % Or less. A desirable addition amount from the viewpoint of magnetic properties is in the range of 0.01 to 0.06%. If the required magnetic property level is not so high, C may be set to 0.01% or less in order to omit or simplify the decarburization in the primary recrystallization annealing.
Si:2.0〜4.5％
Siは、電気抵抗を高めることによって鉄損を改善する有用元素であるが、含有量が4.5％を超えると、冷間圧延性が著しく劣化するので、Siは4.5％以下に限定した。また本発明では、Siを窒化物形成元素として機能させる必要があるため、2.0％以上含有させることが重要である。なお、鉄損の観点からの望ましい添加量は、2.0〜4.5％の範囲である。
Si: 2.0-4.5%
Si is a useful element that improves iron loss by increasing electric resistance. However, if the content exceeds 4.5%, the cold rolling property deteriorates remarkably, so Si is limited to 4.5% or less. In the present invention, Si needs to function as a nitride-forming element, so it is important to contain 2.0% or more. In addition, the desirable addition amount from the viewpoint of iron loss is in the range of 2.0 to 4.5%.
Mn:0.5％以下
Mnは、製造時における熱間加工性を向上させる効果があるので、0.01％以上含有させることが好ましいが、含有量が0.5％を超えた場合には、一次再結晶集合組織が悪化して磁気特性の劣化を招くので、Mnは0.5％以下に限定した。
Mn: 0.5% or less
Mn has the effect of improving the hot workability at the time of production, so it is preferable to contain 0.01% or more. However, if the content exceeds 0.5%, the primary recrystallization texture deteriorates and the magnetic properties are increased. Since the characteristics are deteriorated, Mn is limited to 0.5% or less.
Ｓ，SeおよびＯ:それぞれ50ppm未満
Ｓ，SeおよびＯ量がそれぞれ50ppm以上になると、所望の二次再結晶を得ることが困難となる。この理由は、粗大な酸化物や、スラブ加熱によって粗大化したMnS，MnSeが一次再結晶組織を不均一にするためである。従って、Ｓ，SeおよびＯはいずれも、50ppm未満に抑制するものとした。
S, Se, and O: less than 50 ppm each When the amount of S, Se, and O is 50 ppm or more, it becomes difficult to obtain a desired secondary recrystallization. This is because coarse oxides and MnS and MnSe coarsened by slab heating make the primary recrystallized structure non-uniform. Accordingly, S, Se, and O are all suppressed to less than 50 ppm.
sol.Al:100ppm未満
Alは、表面に緻密な酸化膜を形成し、窒化の際にその窒化量の制御を困難にしたり、脱炭を阻害したりすることがあるため、Alはsol.Al量で100ppm未満に抑制した。但し、酸素親和力の高いAlは、製鋼で微量添加することによって鋼中の溶存酸素量を低減し、鋼板の特性劣化につながる酸化物系介在物の低減などを見込めるため、100ppm未満の範囲で添加することにより磁性劣化を抑制することができる。
sol.Al: less than 100ppm
Al forms a dense oxide film on the surface, which may make it difficult to control the amount of nitridation during nitridation or inhibit decarburization. Therefore, Al is suppressed to less than 100 ppm in terms of sol.Al. did. However, Al with high oxygen affinity can be added in a range of less than 100ppm because it can be added in a small amount in steelmaking to reduce the amount of dissolved oxygen in the steel and reduce oxide inclusions that lead to deterioration of the steel sheet properties. By doing so, magnetic deterioration can be suppressed.
Ｎ:（sol.Al/26.98）×14.00ppm≦Ｎ≦80ppm
本発明は、窒化後、鋼板組織に窒化珪素を析出させることが特徴であるため、含有するAl量に対して、AlNとして析出するＮ以上のＮを事前に含有させておくことが肝要である。すなわちAlNは、原子それぞれが１：１で結合しているため、（sol.Al）量×〔Ｎ原子量(14.00)／Al原子量(26.98)〕以上のＮを含有させておくことで、鋼中に含まれる微量Alを窒化処理前に析出させておくことができる。一方で、スラブ加熱時の「フクレ」などの欠陥の原因となることもあるため、80ppm以下に抑制する必要がある。また望ましくは60ppm以下である。
N: (sol.Al/26.98)×14.00 ppm ≦ N ≦ 80 ppm
Since the present invention is characterized by precipitating silicon nitride in the steel sheet structure after nitriding, it is important to previously contain N equal to or more than N that precipitates as AlN with respect to the amount of Al contained. . That is, since each atom of AlN is bonded at a ratio of 1: 1, it is possible to add N in the amount of (sol.Al) × [N atomic weight (14.00) / Al atomic weight (26.98)] in the steel. A small amount of Al contained in can be deposited before nitriding. On the other hand, since it may cause defects such as “swelling” at the time of slab heating, it must be suppressed to 80 ppm or less. Further, it is desirably 60 ppm or less.
以上、必須成分について説明したが、本発明では、工業的により安定して磁気特性を改善する成分として、以下の元素を適宜含有させることができる。なお、残部は、Feおよび不可避的不純物である。
Ni:0.005〜1.50％
Niは、熱延板組織の均一性を高めることにより、磁気特性を改善する働きがあって、そのためには0.005％以上含有させることが好ましいが、含有量が1.50％を超えると所望の二次再結晶を得ることが困難となり、磁気特性が劣化するので、Niは0.005〜1.50％の範囲で含有させることが望ましい。
The essential components have been described above. In the present invention, the following elements can be appropriately contained as components that improve the magnetic properties more stably industrially. The balance is Fe and inevitable impurities.
Ni: 0.005-1.50%
Ni works to improve the magnetic properties by increasing the uniformity of the hot-rolled sheet structure, and for that purpose, it is preferable to contain 0.005% or more, but if the content exceeds 1.50%, the desired secondary Since it becomes difficult to obtain recrystallization and the magnetic properties deteriorate, it is desirable to contain Ni in the range of 0.005 to 1.50%.
Sn:0.01〜0.50％
Snは、二次再結晶焼鈍中の鋼板の窒化や酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を向上させる有用元素であり、そのためには0.01％以上含有させることが好ましいが、0.50％を超えて含有されると冷間圧延性が劣化するので、Snは0.01〜0.50％の範囲で含有させることが望ましい。
Sn: 0.01-0.50%
Sn is a useful element that suppresses nitriding and oxidation of steel sheets during secondary recrystallization annealing and promotes secondary recrystallization of grains having good crystal orientation to improve magnetic properties. However, if it exceeds 0.50%, the cold rolling property deteriorates, so it is desirable to contain Sn in the range of 0.01 to 0.50%.
Sb:0.005〜0.50％
Sbは、二次再結晶焼鈍中の鋼板の窒化や酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を効果的に向上させる有用元素であり、その目的のためには0.005％以上含有させることが好ましいが、0.50％を超えて含有されると冷間圧延性が劣化するので、Sbは0.005〜0.50％の範囲で含有させることが望ましい。
Sb: 0.005-0.50%
Sb is a useful element that effectively suppresses nitridation and oxidation of steel sheets during secondary recrystallization annealing, promotes secondary recrystallization of grains with good crystal orientation, and effectively improves magnetic properties. For the purpose, it is preferable to contain 0.005% or more, but if it exceeds 0.50%, the cold rolling property deteriorates, so Sb is preferably contained in the range of 0.005 to 0.50%.
Cu:0.01〜0.50％
Cuは、二次再結晶焼鈍中の鋼板の酸化を抑制し、良好な結晶方位を有する結晶粒の二次再結晶を促進して磁気特性を効果的に向上させる働きがあり、そのためには0.01％以上含有させることが好ましいが、0.50％を超えて含有されると熱間圧延性の劣化を招くので、Cuは0.01〜0.50％の範囲で含有させることが望ましい。
Cu: 0.01-0.50%
Cu suppresses oxidation of the steel sheet during secondary recrystallization annealing, promotes secondary recrystallization of grains having a good crystal orientation, and effectively improves magnetic properties. However, if it exceeds 0.50%, the hot rolling property is deteriorated, so it is desirable to contain Cu in the range of 0.01 to 0.50%.
Cr:0.01〜1.50％
Crは、フォルステライト被膜の形成を安定化させる働きがあり、そのためには0.01％以上含有させることが好ましいが、一方でその含有量が1.50％を超えると所望の二次再結晶を得ることが困難となり、磁気特性が劣化するので、Crは0.01〜1.50％の範囲で含有させることが望ましい。
Cr: 0.01 to 1.50%
Cr has a function of stabilizing the formation of the forsterite film, and for that purpose, it is preferable to contain 0.01% or more, but when the content exceeds 1.50%, a desired secondary recrystallization can be obtained. Since it becomes difficult and the magnetic properties deteriorate, it is desirable to contain Cr in the range of 0.01 to 1.50%.
Ｐ:0.0050〜0.50％
Ｐは、フォルステライト被膜の形成を安定化させる働きがあり、そのためには0.0050％以上含有させることが好ましいが、含有量が0.50％を超えると冷間圧延性が劣化するので、Ｐは0.0050〜0.50％の範囲で含有させることが望ましい。
P: 0.0050 ~ 0.50%
P has a function of stabilizing the formation of the forsterite film. For that purpose, P is preferably contained in an amount of 0.0050% or more. However, if the content exceeds 0.50%, the cold rolling property deteriorates, so P is 0.0050 to It is desirable to make it contain in 0.50% of range.
Nb:0.0005〜0.0100％、Mo:0.01〜0.50％
NbおよびMoは、スラブ加熱時の温度変化による割れの抑制等を介して、熱延後のヘゲを抑制する効果を有している。これらの元素は、少なくともどちらか一方を、上記下限値以上含有させなければヘゲ抑制の効果は小さく、一方、どちらかが上記上限を超えると、炭化物や窒化物を形成するなどして最終製品まで残留した際、鉄損劣化を引き起こすため、上述した範囲とすることが望ましい。
Nb: 0.0005-0.0100%, Mo: 0.01-0.50%
Nb and Mo have an effect of suppressing sag after hot rolling through suppression of cracking due to temperature change during slab heating. If these elements do not contain at least one of the above lower limit value or more, the effect of suppressing heges is small. On the other hand, if either of these elements exceeds the above upper limit, carbide or nitride is formed, and the final product. In order to cause deterioration of the iron loss when remaining up to, it is desirable to be in the above range.
次に、本発明の製造方法について説明する。
上記の好適成分組成範囲に調整した鋼スラブを、再加熱することなくあるいは再加熱したのち、熱間圧延に供する。なお、スラブを再加熱する場合には、再加熱温度は、1000℃以上1300℃以下程度とすることが望ましい。というのは、1300℃を超えるスラブ加熱は、スラブの段階で鋼中にインヒビターをほとんど含まない本発明にとって無意味であり、コストアップの要因となるだけである。一方、1000℃未満のスラブ加熱では、熱間圧延時の圧延荷重が高くなって、圧延することが困難になるからである。
Next, the manufacturing method of this invention is demonstrated.
The steel slab adjusted to the above preferable component composition range is subjected to hot rolling without being reheated or after being reheated. When the slab is reheated, the reheating temperature is preferably about 1000 ° C. or higher and 1300 ° C. or lower. This is because slab heating above 1300 ° C is meaningless for the present invention, which contains almost no inhibitor in the steel at the slab stage, and only increases costs. On the other hand, when the slab is heated at a temperature lower than 1000 ° C., the rolling load at the time of hot rolling becomes high and it becomes difficult to perform rolling.
ついで、熱延板に、焼鈍および圧延を施すことによって最終板厚の冷間圧延板とする。具体的には、必要に応じて熱延板焼鈍を施したのち、１回の冷間圧延あるいは中間焼鈍を挟む２回以上の冷間圧延を施して、最終冷延板とする。この冷間圧延は、常温で行ってもよいし、常温より高い温度たとえば250℃程度に鋼板温度を上げて圧延する温間圧延としてもよい。 Next, the hot-rolled sheet is annealed and rolled to obtain a cold-rolled sheet having a final thickness. Specifically, after performing hot-rolled sheet annealing as necessary, it is subjected to one or more cold rollings or two or more cold rollings sandwiching intermediate annealing to obtain a final cold-rolled sheet. This cold rolling may be performed at normal temperature, or may be warm rolling in which the steel sheet temperature is raised to a temperature higher than normal temperature, for example, about 250 ° C.
引続き、最終冷間圧延板に一次再結晶焼鈍を施す。この一次再結晶焼鈍の目的は、圧延組織を有する冷間圧延板を一次再結晶させて、二次再結晶に最適な一次再結晶粒径に調整することである。そのためには、一次再結晶焼鈍の焼鈍温度を800℃以上950℃未満程度とすることが望ましい。なお、この時の焼鈍雰囲気を、湿水素窒素あるいは湿水素アルゴン雰囲気とし、脱炭焼鈍を兼ねても良い。 Subsequently, primary recrystallization annealing is applied to the final cold rolled sheet. The purpose of this primary recrystallization annealing is to adjust the primary recrystallization grain size optimal for secondary recrystallization by primary recrystallization of a cold rolled sheet having a rolled structure. For that purpose, it is desirable to set the annealing temperature of the primary recrystallization annealing to about 800 ° C. or more and less than 950 ° C. Note that the annealing atmosphere at this time may be wet hydrogen nitrogen or wet hydrogen argon atmosphere, and may also serve as decarburization annealing.
本発明における窒素増量のための窒化処理は、冷間圧延後から一次再結晶焼鈍後に焼鈍分離剤を塗布する前、の間で施す。窒化の手法は、増量する窒化量を制御できれば、特に限定しないが、過去に実施されている、例えば、コイル形態のままNH3雰囲気ガスを用いてガス窒化を行う手法や、走行するストリップに対して連続的に窒化を行う手法を採ることができる。また、ガス窒化に比べて窒化能の高い塩浴窒化を利用することも好ましい。 The nitriding treatment for increasing the amount of nitrogen in the present invention is performed after the cold rolling and before the application of the annealing separator after the primary recrystallization annealing. The nitriding method is not particularly limited as long as the amount of nitriding to be increased can be controlled. For example, the nitriding method has been implemented in the past, for example, a method of performing gas nitriding using NH 3 atmosphere gas in a coil form, Thus, it is possible to adopt a method of continuously nitriding. It is also preferable to use salt bath nitriding, which has a higher nitriding ability than gas nitriding.
上記窒化処理の際、重要な点は表層に窒化物層を形成することである。特に、鋼中への拡散を抑制するために800℃以下の温度で窒化を行なうことが望ましいが、時間を短時間（例えば30秒程度）とすることで、高温であっても表面へ窒化物層を形成させることが可能となる。また、窒化による窒素増量は50ppm以上1000ppm以下とするのが肝要である。
窒素増量が50ppm未満では、その効果は十分に得られず、一方、1000ppmを超えると窒化珪素の析出量が過多となって二次再結晶が生じないからである。望ましくは200ppm以上1000ppm以下である。
なお、当該窒素濃度は、たとえ鋼板の一部に濃化していたとしても、鋼板の厚み方向の平均に均した値である。
In the nitriding process, an important point is to form a nitride layer on the surface layer. In particular, it is desirable to perform nitriding at a temperature of 800 ° C. or lower in order to suppress diffusion into the steel, but by reducing the time to a short time (for example, about 30 seconds), the nitride is applied to the surface even at high temperatures. A layer can be formed. In addition, it is important that the nitrogen increase by nitriding is 50 ppm or more and 1000 ppm or less.
This is because if the nitrogen increase is less than 50 ppm, the effect cannot be obtained sufficiently, while if it exceeds 1000 ppm, the amount of silicon nitride deposited becomes excessive and secondary recrystallization does not occur. Desirably, it is 200 ppm or more and 1000 ppm or less.
Note that the nitrogen concentration is a value averaged to the average in the thickness direction of the steel plate even if it is concentrated in a part of the steel plate.
窒化処理後、鋼板表面に焼鈍分離剤を水スラリー化したものを塗布・乾燥する。二次再結晶焼鈍後の鋼板表面にフォルステライト被膜を形成するためには、焼鈍分離剤中の50％以上をMgOとすることが重要である。 After the nitriding treatment, a water slurry of an annealing separator is applied to the steel sheet surface and dried. In order to form a forsterite film on the surface of the steel sheet after secondary recrystallization annealing, it is important that 50% or more of the annealing separator is MgO.
また、本発明では、二次再結晶焼鈍後、フォルステライト中に窒素を窒化物の形で固定するため、焼鈍分離剤中に、ＭをTi、Mn、Si、Cr、AlおよびＢのいずれかとした時のＭの酸化物を、焼鈍分離剤100質量部に対し、ＭＯｘ換算で５質量部以上20質量部以下含ませる必要がある。５質量部以上でないと十分な窒素固定効果が出ない。一方、20質量部よりも多くなるとＭ元素が鋼中に侵入して析出物を形成するなど磁気特性などに悪影響を及ぼすからである。なお、上記ＭＯｘのＭは、Ti、Mn、Si、Cr、AlおよびＢのうち２元素以上が複合し、結果ＭＯｘが複合酸化物であることを妨げない。 In the present invention, after secondary recrystallization annealing, nitrogen is fixed in the form of nitride in forsterite, so that M is any one of Ti, Mn, Si, Cr, Al and B in the annealing separator. It is necessary to include 5 parts by mass or more and 20 parts by mass or less in terms of MOx with respect to 100 parts by mass of the annealing separator. If it is not 5 parts by mass or more, a sufficient nitrogen fixing effect cannot be obtained. On the other hand, if the amount is more than 20 parts by mass, the M element has an adverse effect on the magnetic properties and the like by entering into the steel and forming precipitates. Note that M in the MOx does not prevent that two or more elements of Ti, Mn, Si, Cr, Al, and B are combined, and that the resulting MOx is a composite oxide.
焼鈍分離剤塗布に引続き二次再結晶焼鈍を行なう。本発明における二次再結晶焼鈍では、その昇温過程における300〜800℃間の滞留時間を５時間以上150時間以下とする必要がある。この間に表層の窒化物層は分解して、Ｎが鋼中へ拡散する。特に、AlNを形成することができるAlが残存しない本成分系では、粒界偏析元素であるＮは、粒界を拡散経路として、鋼中へ拡散する。窒化珪素は、鋼とのmisfit率が大きいために、その析出速度は極めて遅い。ここで、窒化珪素の析出は、正常粒成長の抑制が目的であるため、正常粒成長が進行する800℃の段階では十分な量が粒界上に選択的に析出している必要がある。 Following the application of the annealing separator, secondary recrystallization annealing is performed. In the secondary recrystallization annealing in the present invention, the residence time between 300 and 800 ° C. in the temperature raising process needs to be 5 hours or more and 150 hours or less. During this time, the surface nitride layer decomposes and N diffuses into the steel. In particular, in this component system in which Al that can form AlN does not remain, N which is a grain boundary segregation element diffuses into steel using the grain boundary as a diffusion path. Since silicon nitride has a high misfit rate with steel, its precipitation rate is extremely slow. Here, since precipitation of silicon nitride is intended to suppress normal grain growth, a sufficient amount needs to be selectively deposited on the grain boundary at the stage of 800 ° C. where normal grain growth proceeds.
そして、当該温度領域の滞留時間を５時間以上とすることで、窒化珪素は、粒内で析出することはできないものの、粒界を拡散して来たＮと結びつき、粒界上に選択的に析出させることができる。上限については必ずしも設ける必要はないが、150時間を超える焼鈍を行なっても焼鈍に要するエネルギーばかりが必要になるだけなので、150時間以下の時間で行なうこととする。また焼鈍雰囲気としては、Ｎ２、Ar、Ｈ２あるいはこれらの混合ガスのいずれもが適合する。 And by setting the residence time in the temperature region to 5 hours or more, silicon nitride cannot be precipitated in the grains, but is connected to N that has diffused through the grain boundaries, and selectively on the grain boundaries. It can be deposited. Although it is not always necessary to set an upper limit, even if annealing is performed for more than 150 hours, only the energy required for annealing is required. As the annealing atmosphere, any of N 2 , Ar, H 2 or a mixed gas thereof is suitable.
こうしたAl量が抑制され、AlN析出に対して過剰なＮを有しつつ、他のMnS、MnSe等に代表されるインヒビター成分をほとんど含有しないスラブに対して、上述した本発明に従う工程を経て製造された方向性電磁鋼板では、二次再結晶焼鈍昇温過程および二次再結晶開始までの段階において、従来インヒビターに比べて粗大なサイズ（100nm以上）の窒化珪素を粒界に選択的に形成することができる。 Produced through the process according to the present invention described above for slabs in which the amount of Al is suppressed and slabs that contain excess N with respect to AlN precipitation and hardly contain other inhibitor components typified by MnS, MnSe, etc. In the oriented grain-oriented electrical steel sheet, silicon nitride of coarser size (100 nm or more) is selectively formed at grain boundaries compared to conventional inhibitors in the secondary recrystallization annealing temperature raising process and the stage until the start of secondary recrystallization. can do.
図１は、脱炭焼鈍を行なった後、100ppmおよび500ppmの窒化増量が得られるよう窒化処理を行ない300℃〜800℃の滞留時間が８時間となる昇温速度で800℃まで昇温した後、直ちに水冷し、その組織を電子顕微鏡により観察、同定したものである。同図から明らかなように、従来利用されてきた微細析出物（＜100nm）とは異なり、最小のものであっても100nmを超える粗大な窒化珪素が粒界上に析出している様子が確認される。 1 shows that after decarburization annealing, nitriding treatment is performed so that nitriding increase of 100 ppm and 500 ppm can be obtained, and the temperature is raised to 800 ° C. at a heating rate of 300 ° C. to 800 ° C. for a residence time of 8 hours. Immediately cooled with water, the structure was observed and identified with an electron microscope. As is clear from the figure, it is confirmed that coarse silicon nitride exceeding 100 nm is precipitated on the grain boundaries even if it is the smallest, unlike the fine precipitates (<100 nm) used conventionally. Is done.
製造上、窒化珪素の析出には、二次再結晶昇温過程を利用するのがエネルギー効率の観点から、最も有効であることは明白であるが、同様のヒートサイクルを利用すれば窒化珪素の粒界選択析出は可能であるため、長時間の二次再結晶焼鈍の前に、窒化珪素分散焼鈍として、別途の熱処理を実施することも可能である。 From the viewpoint of energy efficiency, it is clear that the secondary recrystallization heating process is most effective for precipitation of silicon nitride in terms of production. However, if a similar heat cycle is used, Since grain boundary selective precipitation is possible, a separate heat treatment can be performed as silicon nitride dispersion annealing before the long-time secondary recrystallization annealing.
上記の二次再結晶焼鈍後、鋼板表面に形成されるフォルステライト被膜には、窒素が１％以上、10％以下含まれるように、主に焼鈍分離剤中のチタン酸化物を制御したり、焼鈍雰囲気を制御したりすることで、被膜中にSi3N4を含ませて調整する。この際、窒素量が１％未満では地鉄部分から十分窒素を純化しきれず磁気特性が劣化する。一方、窒素を10％超含ませると、本発明に従うガラスコーティングであっても、フォルステライト被膜から鋼板への窒素の戻りを防ぐことができなくなるからである。 After the secondary recrystallization annealing, the forsterite film formed on the steel sheet surface mainly controls the titanium oxide in the annealing separator so that nitrogen is contained in an amount of 1% or more and 10% or less. By adjusting the annealing atmosphere, Si 3 N 4 is included in the coating for adjustment. At this time, if the amount of nitrogen is less than 1%, the nitrogen cannot be sufficiently purified from the ground iron portion, and the magnetic properties deteriorate. On the other hand, if more than 10% of nitrogen is contained, even if the glass coating according to the present invention is used, it is not possible to prevent the return of nitrogen from the forsterite film to the steel sheet.
二次再結晶焼鈍後には、鋼板表面にさらにリン酸ガラスを主体とするガラスコーティングを塗布、焼付けする。その際の、ガラスコーティング液は、リン酸塩化合物と、ＡをAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのいずれかとしたＡの酸化物を１種または２種以上とを含み、かつ該酸化物の金属成分Ａの合計：Ｚ（mol）と、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）が0.08≦Z/P≦0.8の関係を満足したものとすることが肝要である。なお、上記Ａは、Al、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのうち２元素以上が複合し、Ａの酸化物が複合酸化物であることを妨げない。 After the secondary recrystallization annealing, a glass coating mainly composed of phosphate glass is further applied and baked on the steel plate surface. In this case, the glass coating liquid is composed of a phosphate compound and one or two oxides of A in which A is any of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn. And the molar ratio (Z / P) of the total of metal components A of the oxide : Z (mol) to phosphorus: P (mol) in the phosphate compound is 0.08 ≦ Z / P It is important to satisfy the relationship of ≦ 0.8. The above A does not prevent that two or more elements of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn are combined, and the oxide of A is a composite oxide.
このガラスコーティングの機能の一つとして低熱膨張係数による鋼板への張力付与があり、その目的でシリカを添加しリン酸-シリカ系ガラスとすることが好ましく、シリカの添加量はガラス組成を各元素の酸化物で表したときにモル％で40mol％以上とすることが好ましい。 One of the functions of this glass coating is to impart tension to the steel sheet with a low coefficient of thermal expansion, and for that purpose, it is preferable to add silica to form a phosphoric acid-silica glass. The amount of silica added depends on the glass composition. When expressed in terms of oxide, it is preferably 40 mol% or more in terms of mol%.
また、上記コーティングの塗布や、焼付けの条件としては、常法を用いることができるが、例えば、塗布の手段としては、ロールコーターやスプレーコーターを用いる手段が、また焼付けの条件としては、800〜1000℃の範囲で１〜２分間などが挙げられる。
かかる工程を経ることで、本発明に従う方向性電磁鋼板および方向性電磁鋼板用表面ガラスコーティングが得られるのである。
さらに、本発明では、平坦化焼鈍により、鋼板の形状を整えることが可能であり、この平坦化焼鈍を、絶縁被膜の焼付け処理と兼ねることもできる。
In addition, as a condition for application of the coating and baking, a conventional method can be used. For example, as a means for application, a means using a roll coater or a spray coater, and as a condition for baking, 800 to Examples include 1 to 2 minutes in the range of 1000 ° C.
By passing through this process, the grain-oriented electrical steel sheet and the surface glass coating for the grain-oriented electrical steel sheet according to the present invention are obtained.
Furthermore, in the present invention, the shape of the steel sheet can be adjusted by flattening annealing, and this flattening annealing can also serve as a baking treatment of the insulating coating.
上記の絶縁被膜の焼付け処理（ガラスコーティング）の際、リン酸塩化合物と、ＡをAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのいずれかとしたＡの酸化物を１種または２種以上含み、かつ該酸化物の金属成分Ａの合計：Ｚ（mol）と、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）が0.08≦Z/P≦0.8の関係を満足させる必要があるのは、前述したとおりである。
上記Z/Pが0.08未満であると、ガラスコーティングによるフォルステライト中の窒化物の安定化効果が無く、一方、Z/Pが0.8よりも大きいと、ガラス転移温度の上昇によってガラスコーティングの形成が困難になったり、そもそもガラス化しなくなったりするからである。従って、本発明では、ガラスコーティング中のリン成分と、ガラスコーティング中の上記Ａの合計：Ｚとのモル比を、0.08以上0.8以下とすることが重要である。
At the time of baking treatment (glass coating) of the insulating film, a phosphate compound and an oxide of A in which A is any of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn The molar ratio (Z / P) of the total of the metal component A of the oxide : Z (mol) and phosphorus: P (mol) in the phosphate compound is 0.08 ≦ As described above, it is necessary to satisfy the relationship of Z / P ≦ 0.8.
If the Z / P is less than 0.08, there is no effect of stabilizing the nitride in the forsterite by the glass coating, while if Z / P is greater than 0.8, the glass transition temperature is increased to form a glass coating. This is because it becomes difficult or it does not vitrify in the first place. Therefore, in the present invention, it is important that the molar ratio of the phosphorus component in the glass coating and the total of A in the glass coating: Z is 0.08 or more and 0.8 or less.
（実施例１）
Si：3.3％、Ｃ：0.06％、Mn：0.08％、Ｓ：0.001％、Al：0.002％、Ｎ：0.002％、Cu：0.05％およびSb：0.01％を含有する珪素鋼板スラブを、1100℃、30分加熱後、熱間圧延して2.2mmの板厚の熱延板とし、1000℃、１分間の焼鈍を施した後、冷間圧延により0．23mmの最終板厚とし、得られた冷間圧延コイルの中央部から、100mm×400mmサイズの試料を採取し、ラボにて一次再結晶焼鈍と脱炭および窒化（連続窒化処理）を兼ねた焼鈍をおこなった。窒化処理はH2-NH3混合ガスによるガス窒化処理を750℃、20秒行った。窒素量は、全厚を対象としたもので300ppm、表層（両面）各３μmをサンドペーパーで削り、表層を除いた状態で25ppmであった。引続き、TiO2を10質量部混合したMgOを主体とする焼鈍分離剤を水スラリー状にしてから塗布、乾燥した。この鋼板に対し、300℃から800℃間を100時間かけて昇温させた後、1200℃まで50℃/ｈで昇温させ、1200℃で５時間焼鈍する二次再結晶焼鈍を行った。二次再結晶焼鈍で形成されたフォルステライト被膜中の窒素量は2.7％、地鉄中窒素量は10ppmであった。
続いてリン酸塩系のガラスコーティングを表１に記載の組成（各金属酸化物換算で固形分換算mol％）で混合したコーティング液を鋼板に塗布し、800℃、1分で焼付け、コーティング形成の良否や、磁化力800A/mでの磁束密度（Ｂ８，Ｔ）、1.7Ｔ、50Hz励磁での鉄損（Ｗ17/50，W/kg）をそれぞれ測定し、歪取焼鈍後の磁性劣化確認試験として、850℃で10時間、窒素雰囲気下における焼鈍した後の鉄損（Ｗ17/50，W/kg）および地鉄窒素量（ppm）を評価した。
測定および評価結果を表１に併記する。
Example 1
A silicon steel plate slab containing Si: 3.3%, C: 0.06%, Mn: 0.08%, S: 0.001%, Al: 0.002%, N: 0.002%, Cu: 0.05% and Sb: 0.01%, After heating for 30 minutes, hot rolled into a hot rolled sheet with a thickness of 2.2 mm, annealed at 1000 ° C. for 1 minute, and then cold rolled to a final sheet thickness of 0.23 mm. A sample with a size of 100 mm × 400 mm was taken from the center of the cold rolled coil and subjected to primary recrystallization annealing, decarburization, and nitriding (continuous nitriding treatment) in a laboratory. Nitriding treatment was performed by gas nitriding treatment with H 2 —NH 3 mixed gas at 750 ° C. for 20 seconds. The amount of nitrogen was 300 ppm for the total thickness, and 25 ppm when the surface layer (both sides) was 3 μm each shaved with sandpaper and the surface layer was removed. Subsequently, an annealing separator mainly composed of MgO mixed with 10 parts by mass of TiO 2 was made into a water slurry, and then applied and dried. The steel sheet was heated from 300 ° C. to 800 ° C. over 100 hours, then heated to 1200 ° C. at 50 ° C./h, and subjected to secondary recrystallization annealing in which annealing was performed at 1200 ° C. for 5 hours. The amount of nitrogen in the forsterite film formed by secondary recrystallization annealing was 2.7%, and the amount of nitrogen in the ground iron was 10 ppm.
Subsequently, a coating solution in which phosphate glass coating is mixed with the composition shown in Table 1 (mol% in terms of solid content in terms of each metal oxide) is applied to the steel plate and baked at 800 ° C for 1 minute to form the coating. , Magnetic flux density (B 8 , T) at a magnetizing force of 800 A / m, iron loss (W 17/50 , W / kg) at 1.7 T, 50 Hz excitation, and magnetism after strain relief annealing As a deterioration confirmation test, the iron loss (W 17/50 , W / kg) and the amount of nitrogen (ppm) after annealing in a nitrogen atmosphere at 850 ° C. for 10 hours were evaluated.
The measurement and evaluation results are also shown in Table 1.
同表に示したとおり、本発明に従う発明例では、歪取焼鈍における鉄損劣化がほとんど認められず、地鉄窒素純化も良好なことが分かる。 As shown in the table, in the inventive examples according to the present invention, it is understood that the iron loss deterioration in the strain relief annealing is hardly observed, and that the purification of the ground iron nitrogen is good.
（実施例２）
Si：3.3％、Ｃ：0.06％、Mn：0.08％、Ｓ：0.001％、Al：0.002％、Ｎ：0.002％、Cu：0.05％およびSb：0.01％を含有する珪素鋼板スラブを、1100℃、30分加熱後、熱間圧延して2.2mmの板厚の熱延板とし、1000℃、１分間の焼鈍を施した後、冷間圧延により0.23mmの最終板厚とし、得られた冷間圧延コイルの中央部から、100mm×400mmサイズの試料を採取し、ラボにて一次再結晶と脱炭焼鈍を行なった。その後、表２に記載の窒化処理を行った。窒素量（全厚）は表２のとおりであった。引続き、表２に示した割合でTiO2を混合したMgOを主体とする焼鈍分離剤を、水スラリー状にしてから塗布、乾燥した。この鋼板に対し300℃から800℃間を100時間かけて昇温させた後、1200℃まで50℃/ｈで昇温させ、1200℃で５時間焼鈍する最終仕上げ焼鈍を行った。二次再結晶焼鈍で形成されたフォルステライト被膜中の窒素量、地鉄中窒素量を表２に併記する。
次に、リン酸ガラスを主体とするガラスコーティングを、表２に記載の組成（各金属酸化物換算で固形分換算mol％）で混合したコーティング液を用いて、塗布し、800℃で１分焼付けることで鋼板表面に形成した。
ついで、上記鋼板の磁化力800A/mでの磁束密度（Ｂ８，Ｔ）や、1.7Ｔ、50Hz励磁での鉄損（Ｗ17/50，W/kg）を測定し、さらに、歪取焼鈍後の磁性劣化確認試験として850℃、10時間窒素雰囲気下で焼鈍した後の鉄損（Ｗ17/50，W/kg）や、地鉄窒素量（ppm）をそれぞれ評価した。
測定および評価結果を表２に併記する。
(Example 2)
A silicon steel plate slab containing Si: 3.3%, C: 0.06%, Mn: 0.08%, S: 0.001%, Al: 0.002%, N: 0.002%, Cu: 0.05% and Sb: 0.01%, After 30 minutes of heating, hot rolled to a hot rolled sheet with a thickness of 2.2 mm, annealed at 1000 ° C. for 1 minute, and then cold rolled to a final sheet thickness of 0.23 mm. A sample of 100 mm × 400 mm size was taken from the center of the rolled coil and subjected to primary recrystallization and decarburization annealing in the laboratory. Thereafter, the nitriding treatment described in Table 2 was performed. The amount of nitrogen (total thickness) was as shown in Table 2. Subsequently, an annealing separator mainly composed of MgO mixed with TiO 2 at a ratio shown in Table 2 was formed into a water slurry, and then applied and dried. The steel sheet was heated from 300 ° C. to 800 ° C. over 100 hours, then heated to 1200 ° C. at 50 ° C./h, and final finish annealing was performed by annealing at 1200 ° C. for 5 hours. The amount of nitrogen in the forsterite film formed by secondary recrystallization annealing and the amount of nitrogen in the ground iron are also shown in Table 2.
Next, a glass coating mainly composed of phosphate glass was applied using a coating solution in which the composition shown in Table 2 was mixed with the composition shown in Table 2 (mol% in terms of solid content in terms of each metal oxide), and then at 800 ° C. for 1 minute. It was formed on the steel sheet surface by baking.
Next, the magnetic flux density (B 8 , T) of the steel sheet at 800 A / m and the iron loss (W 17/50 , W / kg) at 1.7 T and 50 Hz excitation are measured, and further, strain relief annealing is performed. As a subsequent magnetic deterioration confirmation test, the iron loss (W 17/50 , W / kg) after annealing in a nitrogen atmosphere at 850 ° C. for 10 hours and the amount of nitrogen (ppm) in the steel were evaluated.
The measurement and evaluation results are also shown in Table 2.
同表に記載のとおり、本発明に従う発明例では、磁気特性の劣化が殆ど無く、地鉄窒素純化も良好なことが分かる。 As shown in the table, in the inventive examples according to the present invention, it is understood that there is almost no deterioration of magnetic properties and that the purification of the ground iron nitrogen is good.
（実施例３）
表３に示す成分を含有する珪素鋼板スラブを、1200℃で20分の加熱後、熱間圧延して2.0mmの板厚の熱延板とし、1000℃、１分の焼鈍を施した後、冷間圧延により板厚：1.5mmまでの冷間圧延後、1100℃、２分の中間焼鈍を施し、以下に示す冷間圧延により0.27mmの最終板厚としてから、PH2O/PH2＝0.3の雰囲気下、焼鈍温度：820℃となる条件で２分間保持し脱炭焼鈍を行なった。その後、一部コイルに対してバッチ処理で窒化処理（NH3雰囲気下）を行ない、鋼中Ｎ量を550ppm増量させた後、MgOを主成分として、表３に記載の酸化物を添加した焼鈍分離剤を水と混ぜてスラリー状としたものを塗布した後、コイルに巻き取り、300〜800℃間の滞留時間が30時間となる昇温速度で焼鈍を行った。続いて、コロイド状シリカをSiO2として46.2mol％、リン酸マグネシウムをMg(PO３)２として30.8mol％、Al2O3を23.1mol％含んだコーティング液（Z/P値：0.75）を塗布し、焼付けた。さらに鋼帯の平坦化を目的とする平坦化焼鈍を施して製品とした。
かようにして得られた製品コイルからエプスタイン試験片を採取して、磁束密度（Ｂ８）や、1.7Ｔ、50Hz励磁での鉄損（Ｗ17/50，W/kg）、被膜中窒素量（％）を測定し、さらに歪取焼鈍後の磁性劣化確認試験として850℃で10時間の窒素雰囲気による焼鈍を施した後の鉄損（Ｗ17/50，W/kg）および地鉄窒素量（ppm）を評価した。
測定および評価結果を表３に併記する。
(Example 3)
After heating the silicon steel plate slab containing the components shown in Table 3 at 1200 ° C. for 20 minutes, hot rolling to a hot-rolled sheet with a thickness of 2.0 mm, annealing at 1000 ° C. for 1 minute, Thickness by cold rolling: Cold rolling to 1.5mm, intermediate annealing at 1100 ° C for 2 minutes, and final rolling thickness of 0.27mm by cold rolling shown below, PH 2 O / PH 2 = In an atmosphere of 0.3, decarburization annealing was performed by maintaining the annealing temperature at 820 ° C. for 2 minutes. After that, nitriding treatment (under NH 3 atmosphere) was performed on some coils by batch treatment, increasing the amount of N in the steel by 550 ppm, and then annealing by adding MgO as the main component and the oxides listed in Table 3 After applying a separating agent mixed with water to form a slurry, it was wound on a coil and annealed at a temperature rising rate at which the residence time between 300-800 ° C. was 30 hours. Subsequently, a coating solution (Z / P value: 0.75) containing 46.2 mol% of colloidal silica as SiO 2 , 30.8 mol% of magnesium phosphate as Mg (PO 3 ) 2 and 23.1 mol% of Al 2 O 3 was used. Applied and baked. Furthermore, the product was subjected to flattening annealing for the purpose of flattening the steel strip.
An Epstein test piece is taken from the product coil thus obtained, magnetic flux density (B 8 ), iron loss (W 17/50 , W / kg) at 1.7 T, 50 Hz excitation, and nitrogen content in the coating (%), And iron loss (W 17/50 , W / kg) and amount of ground iron nitrogen after annealing in nitrogen atmosphere for 10 hours at 850 ° C as a magnetic deterioration confirmation test after strain relief annealing (Ppm) was evaluated.
The measurement and evaluation results are also shown in Table 3.
同表に記載のとおり、本発明に従う発明例では歪み取り焼鈍後の磁気特性も良好で、地鉄窒素純化も良好であることが分かる。
As shown in the table, it can be seen that in the inventive examples according to the present invention, the magnetic properties after the strain relief annealing are also good and the nitrogen purification is good.
Claims (4)
上記焼鈍分離剤が、MgOを50％以上含有し、かつＭをTi、Mn、Si、Cr、AlおよびＢのいずれかとした時のＭの酸化物を、焼鈍分離剤100質量部に対し、ＭＯｘ換算で５質量部以上20質量部以下含有し、さらに
上記ガラスコーティング液が、リン酸塩化合物と、ＡをAl、Ca、Ti、Nd、Mo、Cr、Ｂ、Ta、CuおよびMnのいずれかとしたＡの酸化物を１種または２種以上とを含み、かつ該酸化物の金属成分Ａの合計：Ｚ（mol）と、上記リン酸塩化合物中のリン：Ｐ（mol）とのモル比（Z/P）が0.08≦Z/P≦0.8の関係を満足することを特徴とする方向性電磁鋼板の製造方法。 In addition to containing C: 0.08% or less, Si: 2.0 to 4.5%, and Mn: 0.5% or less, S, Se, and O are each suppressed to less than 50 ppm by mass, and sol.Al is suppressed to less than 100 ppm by mass. Further, N is controlled in the range of [acid-soluble Al (sol.Al) mass ppm / 26.98] × 14.00 ≦ N ≦ 80 mass ppm, and the remainder is reheated to a steel slab having a composition of Fe and inevitable impurities. Without re-heating or after re-heating, hot-rolled sheet is used to make a cold-rolled sheet with the final thickness by annealing and rolling. After performing nitriding treatment to a mass ppm or less, an annealing separator is applied, and in the temperature raising process of secondary recrystallization annealing, the residence time between 300-800 ° C. is set to 5 hours or more and 150 hours or less. After the next recrystallization annealing, the glass separator is removed by removing the annealing separator and baking. In the production of a series of grain-oriented electrical steel sheet to form a glass coating on the steel sheet surface mainly comprising,
The above-mentioned annealing separator contains 50% or more of MgO, and M is an oxide of M when M is any one of Ti, Mn, Si, Cr, Al and B with respect to 100 parts by mass of the annealing separator. 5 parts by weight or more and 20 parts by weight or less in terms of conversion, and the glass coating solution further comprises a phosphate compound and A as one of Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn. 1 or 2 or more, and the total of metal components A of the oxide: molar ratio of Z (mol) and phosphorus in the phosphate compound : P (mol) (Z / P) satisfies the relationship of 0.08 ≦ Z / P ≦ 0.8. A method for producing a grain-oriented electrical steel sheet, wherein:
Ni：0.005〜1.50％、
Sn：0.01〜0.50％、
Sb：0.005〜0.50％、
Cu：0.01〜0.50％、
Cr：0.01〜1.50％、
Ｐ：0.0050〜0.50％、
Mo：0.01〜0.50％および
Nb：0.0005〜0.0100％
のうちから選んだ１種または２種以上を含有することを特徴とする請求項１に記載の方向性電磁鋼板の製造方法。 Furthermore, the said steel slab is mass%,
Ni: 0.005-1.50%,
Sn: 0.01 to 0.50%,
Sb: 0.005-0.50%,
Cu: 0.01 to 0.50%,
Cr: 0.01 to 1.50%,
P: 0.0050 to 0.50%,
Mo: 0.01-0.50% and
Nb: 0.0005-0.0100%
The method for producing a grain-oriented electrical steel sheet according to claim 1, comprising one or more selected from among the above.
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