WO2014047757A1 - 一种高磁感普通取向硅钢的制造方法 - Google Patents

一种高磁感普通取向硅钢的制造方法 Download PDF

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WO2014047757A1
WO2014047757A1 PCT/CN2012/001682 CN2012001682W WO2014047757A1 WO 2014047757 A1 WO2014047757 A1 WO 2014047757A1 CN 2012001682 W CN2012001682 W CN 2012001682W WO 2014047757 A1 WO2014047757 A1 WO 2014047757A1
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rolling
magnetic induction
content
silicon steel
oriented silicon
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PCT/CN2012/001682
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English (en)
French (fr)
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沈侃毅
李国保
储双杰
孙业中
章华兵
杨勇杰
胡卓超
赵斌
徐琪
黄杰
章培莉
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宝山钢铁股份有限公司
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Priority to RU2015108466A priority Critical patent/RU2609605C2/ru
Priority to KR1020157007230A priority patent/KR20150043504A/ko
Priority to JP2015533391A priority patent/JP6461798B2/ja
Priority to MX2015003320A priority patent/MX366340B/es
Priority to EP12885574.9A priority patent/EP2902507B1/en
Priority to US14/430,463 priority patent/US9905361B2/en
Publication of WO2014047757A1 publication Critical patent/WO2014047757A1/zh

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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
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    • H01F1/147—Alloys characterised by their composition
    • H01F1/14766—Fe-Si based alloys
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    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/05—Grain orientation

Definitions

  • the present invention relates to a method of manufacturing a metal alloy, and more particularly to a method of manufacturing an iron-based alloy. Background technique
  • the conventional Oriented Silicon Steel is manufactured by secondary cold rolling method using MnS or MnSe as an inhibitor.
  • the main production process is - smelting ⁇ hot rolling - normalization ⁇ primary cold rolling ⁇ intermediate annealing ⁇ Secondary cold rolling ⁇ decarburization annealing ⁇ high temperature annealing ⁇ insulating coating.
  • the technical point is - smelting: steelmaking by converter (or electric furnace), secondary refining and alloying, continuous casting into slab, the basic chemical composition mass percentage is Si: 2.5 ⁇ 4.5%, C: 0.02- 0.10%, Mn: 0.025 ⁇ 0.25%, S or Se: 0.01 ⁇ 0.035%, Al ⁇ O.01%, ⁇ O.005%, and some component systems also contain elements such as Cu, Mo, Sb, B, Bi, etc. One or more, the rest are iron and inevitable impurity elements.
  • Hot rolling Generally, the slab is heated to a temperature of 1350 ° C or higher in a special high-temperature heating furnace, and is kept for more than 45 minutes to fully dissolve the favorable inclusions MnS or MnSe, and then carry out 4 to 6 passes. Rough rolling and finish rolling. The rapid cooling between the finish rolling and the coiling allows the carbide to be dispersed in the grains, which is advantageous for obtaining fine and uniform primary grains in the future.
  • the cold rolling reduction rate is 60 to 70%, and is rolled by 3 to 4 passes.
  • Intermediate annealing The intermediate annealing temperature is 850 to 950 ° C, and the annealing time is 2.5 to 4.0 minutes.
  • Secondary cold rolling The secondary cold rolling reduction after intermediate annealing is 50 to 55%, and the cold rolling pass is 2 to 3 passes.
  • Decarburization annealing Primary recrystallization is performed by decarburization annealing to form secondary grain nucleation sites. The C content is removed to below 30 ppm to ensure a single a-phase during high-temperature annealing, and a perfect secondary recrystallized structure is developed to eliminate the magnetic aging of the finished product.
  • High-temperature annealing It must be subjected to high-temperature annealing for secondary recrystallization and secondary grain growth, and then a layer of magnesium silicate underlayer glass film is formed on the surface of the strip. Finally, purification and annealing removes sulfur and nitrogen decomposed by the inhibitor. Ordinary oriented silicon steel with high degree of orientation and ideal magnetic properties is obtained for elements harmful to magnetic properties.
  • Insulating Coating An oriented silicon steel product obtained by applying an insulating coating and tensile annealing to obtain a commercial application form.
  • the publication No. CN1321787A published on November 14, 2001, entitled “Single-Oriented Electrical Steel Sheet and Its Preparation Method", discloses a single-oriented electrical steel sheet and a method for producing the same.
  • the manufacturing process of the method comprises: smelting the raw material, the chemical composition content percentage is C: 0.02-0.15%, Si: 1.5 2.5% Mn: 0.02-0.20%, acid-soluble Al; 0.015 0.065% N: 0.0030 0.0150%, the total amount of one or two selected from S and Se: 0.005 0.040%, the balance is Fe and other impurities which are unavoidable; the hot rolled coil annealing is performed once at 900 1100 °C.
  • the object of the present invention is to provide a method for manufacturing a high magnetic induction ordinary oriented silicon steel, which can obtain a higher magnetic field by using only one time aging rolling without the need for normalization, intermediate annealing and the like.
  • Sense (B8 ⁇ 1.88T) of ordinary oriented silicon steel is to provide a method for manufacturing a high magnetic induction ordinary oriented silicon steel, which can obtain a higher magnetic field by using only one time aging rolling without the need for normalization, intermediate annealing and the like.
  • the present invention provides a method of manufacturing a high magnetic induction ordinary oriented silicon steel comprising the following steps:
  • Hot rolling heating temperature is 1090 ⁇ 1200 °C;
  • Nitriding treatment the infiltration nitrogen content [N] D satisfies 328 - 0.14 a - 0.85 b - 2.33 c ⁇ [N] D ⁇ 362 - 0.16 a - 0.94 b - 2.57 c; wherein a is the smelting step Als Content, the unit is ppm; b is the content of N element in the smelting step, the unit is ppm; c is the primary grain size, the unit is ⁇ ⁇ ;
  • the inventors have found through extensive experiments that proper control of the nitrogen content during the steel making process can obtain a product with higher magnetic induction, and can eliminate the processes of normalization and intermediate annealing, and convert the secondary cold rolling method to a cold one.
  • the rolling method shortens the production cycle and significantly increases the production efficiency. Since in this technical solution, after the decarburization annealing process, nitriding treatment is required, it is necessary to control the niobium content in the smelting stage. In the lower range, so as to avoid heating with high temperature, the technical solution adopts the low temperature slab heating technology of 1090 ⁇ 1200 °C for manufacturing.
  • the nitriding treatment in the technical solution is directed to the low temperature slab heating technology in the technical solution, which nitridizes the cold rolled decarburized sheet to supplement the strength of the insufficient inhibitor in the substrate, and the added inhibitor is
  • the amount of secondary inhibitor specially prepared for secondary recrystallization directly determines the degree of perfection of secondary recrystallization of the decarburized steel sheet during high temperature annealing.
  • the strength of the inhibitor is weakened, and the secondary recrystallization nucleus is extended to the plate thickness direction, not only the sharp Gaussian orientation of the near surface layer of the steel sheet, but also the normal crystal of the center layer.
  • the grain also undergoes secondary recrystallization, which causes the degree of orientation to deteriorate, and the magnetic properties are deteriorated, so that the B 8 of the finished product is lowered.
  • secondary recrystallization causes the degree of orientation to deteriorate, and the magnetic properties are deteriorated, so that the B 8 of the finished product is lowered.
  • the nitrogen content in the nitriding treatment is excessive, the Gaussian orientation is extremely deteriorated, and the metal defects are exposed on the magnesium silicate glass film formed during the high-temperature annealing, and the defect rate is remarkably increased.
  • the nitrogen content of the nitriding treatment should satisfy the relationship: 328 - 0.14 a - 0.85 b - 2.33 c [N] D ⁇ 362 - 0.16 a - 0.94 b - 2.57 c (a is the content of Als in the smelting step, ppm b is the content of N element in the smelting step, ppm; c is the initial grain size, ⁇ ⁇ ).
  • the cold rolling reduction ratio is controlled to be 80%.
  • the temperature increase rate is controlled to 15 to 35 ° C / s
  • the decarburization temperature is 800 to 860 ° C
  • the decarburization dew point is 60 to 70 ° C.
  • the nitrogen content of the nitriding treatment under the premise of reducing the production process, obtains the ordinary oriented silicon steel with higher magnetic induction (B8 1.88T), which not only saves the production process, improves the production efficiency, but also guarantees Ordinary oriented silicon steel has ideal magnetic properties and excellent orientation.
  • the steel is converted by a converter or an electric furnace, and the molten steel is subjected to secondary refining, and a slab is obtained after continuous casting, and the chemical element mass percentage thereof is: C: 0.02-0.08%, Si: 2.0-3.5%, Mn: 0.05-0.20%, S: 0.005 to 0.012%, Als: 0.010 to 0.060%, N: 0.002 to 0.014%, Sn: 0.10%, and the balance is Fe and other unavoidable impurities.
  • the different components in the slab after hot rolling is heated to a 1150 ° C hot rolled sheet having a thickness of 2. 3mm, the initial pass and finish rolling temperature is 1070 ° C respectively and 935 ° C, coiling temperature 636 ° C.
  • the hot rolled sheet After the hot rolled sheet is pickled, it is cold rolled once to a thickness of 0.30 mm.
  • the decarburization annealing rate is 25 ° C / s, the decarburization temperature is 845 ° C, and the decarburization dew point is 67 ° C.
  • Decarburization annealing is performed to reduce the [C] content in the steel sheet to 30 ppm or less.
  • Nitriding treatment process 780X 30sec, oxidation degree P3 ⁇ 4o/P3 ⁇ 4 is 0.065, ⁇ 3 dosage is 3.2wt%, and infiltration [N] content is 160ppm.
  • high temperature annealing After coating a separator containing MgO as a main component, high temperature annealing is performed in a bell furnace. After unwinding, after coating with insulating coating and tensile flat annealing, the finished product and production cycle are shown in Table 1.
  • the steel is converted by a converter or an electric furnace, and the molten steel is subjected to secondary refining, and a slab is obtained after continuous casting.
  • the chemical element mass percentage is Si: 3.0%, C: 0.05%, Mn: 0.11%, S: 0.007%, Als: 0.03%, N: 0.007%, Sn: 0.06%, the balance being Fe and unavoidable impurities; then hot rolling, different hot rolling process conditions are shown in Table 2 below.
  • the hot rolled sheet is pickled and once cooled to a finished thickness of 0.30 mm.
  • the decarburization annealing rate is 25 ° C / s
  • the decarburization temperature is 840 ° C
  • the decarburization dew point is 70 ° C.
  • Decarburization annealing is performed to reduce the [C] content in the steel sheet to 30 ppm or less.
  • Nitriding treatment process 800 ° C x 30 sec, oxidation degree PH 2 O / P3 ⁇ 4 is 0.14, NH 3 dosage l. lwt%, infiltration [N] content 200ppm.
  • high temperature annealing is performed in a hood furnace. After unwinding, after coating the insulating coating and stretching and flat annealing, the obtained finished product B 8 is shown in Table 2.
  • Example 4 1090 ° C 1060 945 576 1.88
  • Example 5 1200 ° C 1070 880 628 1.89
  • Example 6 1150 ° C 1180 940 564 1.89
  • Example 7 1130 ° C 1050 860 550 1.88
  • the steel is converted by a converter or an electric furnace, and the molten steel is subjected to secondary refining, and a slab is obtained after continuous casting.
  • the chemical element mass percentage is Si: 2.8%, C: 0.04%, S: 0.009%, Als: 0.04%, N: 0.005%, Mn: 0.10%, Sn: 0.03%, and the balance is Fe and unavoidable impurities.
  • the slab was heated at 1,130 ° C and then hot rolled to a hot rolled sheet having a thickness of 2.5 mm.
  • the rolling and finishing temperatures were 1080 ° C and 920 ° C, respectively, and the coiling temperature was 605 ° C.
  • the hot rolled sheet was pickled, cold rolled to a thickness of 0.35 mm, and then subjected to decarburization annealing.
  • the different decarburization annealing conditions are shown in Table 3 below.
  • the [C] content in the steel sheet was lowered to 30 ppm or less.
  • Nitriding annealing process 800 ° C x 30 sec, oxidation degree PH 2 O / P3 ⁇ 4 is 0.15, NH 3 dosage is 0.9 wt%, and the [N] content is 170 ppm.
  • high temperature annealing is performed in a bell furnace. After unwinding, after coating with an insulating coating and stretching and flat annealing, the obtained finished product B 8 is shown in Table 3.
  • the steel is converted by a converter or an electric furnace, and the molten steel is subjected to secondary refining, and a slab is obtained after continuous casting.
  • the chemical element mass percentage is Si: 3.0%, C: 0.05%, Mn: 0.11%, S: 0.007%, Als: 0.03%, N: 0.007%, Sn: 0.06%, the balance being Fe and unavoidable impurities.
  • the slab was heated at 1120 ° C and hot rolled to a hot rolled sheet having a thickness of 2.5 mm.
  • the rolling and final temperatures were 1080 ° C and 920 ° C, respectively, and the coiling temperature was 605 ° C.
  • the hot rolled sheet was pickled and cold rolled to a finished thickness of 0.35 mm.
  • decarburization annealing was carried out at a temperature rising rate of 30 ° C / SeC , a decarburization temperature of 840 ° C, and a decarburization dew point of 68 ° C.
  • Nitriding treatment is then carried out, and the different nitriding annealing process conditions are as shown in Table 4 below.
  • high temperature annealing is performed in a bell furnace. After unwinding, after coating with an insulating coating and stretching and flat annealing, the obtained finished product B 8 is shown in Table 4.
  • the steel is transformed by a converter ⁇ electric furnace, and the molten steel is subjected to secondary refining, and a slab is obtained after continuous casting.
  • the chemical element mass percentage is Si: 2.8%, C: 0.045%, Mn: 0.06%, S: 0.009%, Als : 0.024%, N: 0.009%, Sn: 0.04%, the balance being Fe and unavoidable impurities.
  • the slab was heated at 1120 ° C and hot rolled to a hot rolled sheet having a thickness of 2.3 mm.
  • the rolling and finishing temperatures were 1070 ° C and 900 ° C, respectively, and the coiling temperature was 570 ° C.
  • the hot rolled sheet was pickled and cold rolled to a finished thickness of 0.30 mm.
  • decarburization annealing was carried out at a temperature rising rate of 20 ° C / S ec , a decarburization temperature of 830 ° C, and a decarburization dew point of 70 ° C.
  • Nitriding treatment is then carried out, and the effect of different infiltration nitrogen contents on the finished product B 8 is shown in Table 5 below.
  • high temperature annealing is performed in a bell furnace. After unwinding, after coating with an insulating coating and stretching and flat annealing, the obtained B 8 is shown in Table 5.
  • Table 5 reflects the effect of the infiltration nitrogen content on the finished product. It can be seen from Table 5 that the infiltrated nitrogen content needs to satisfy the infiltrated nitrogen content calculated according to the Als content a, N content b and the primary grain size c in the smelting stage [N] D (328 - 0.14 a - 0.85 b - 2.33 c ⁇ [N] D ⁇ 362 - 0.16 a - 0.94 b - 2.57 c) 0
  • the actual nitriding amount is within the calculated value range, as in Examples 24-29, the magnetic induction of the finished product is higher; otherwise, as in Comparative Example 20 -25, the finished product has a low magnetic induction.

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Abstract

一种磁感应B8≥1.88T的取向硅钢的制造方法，其包括以下步骤：1）冶炼、连铸后获得板坯，控制冶炼阶段的N含量为0.002-0.014wt%；2）热轧；3）冷轧；4）脱碳退火；5）氮化处理：控制渗入氮含量[N]D满足：328-0.14a-0.85b-2.33c≤[N]D≤362-0.16a-0.94b-2.57c，式中，a为冶炼步骤中Als的含量，ppm；b为N元素的含量，ppm；c为初次晶粒尺寸，μm；6）表面涂覆氧化镁涂层，进行退火；7）涂覆绝缘涂层。

Description

一种高磁感普通取向硅钢的制造方法 技术领域
本发明涉及一种金属合金制造方法，尤其涉及一种铁基合金的制造方法。 背景技术
通常现有普通取向硅钢 (CGO)是以 MnS或 MnSe为抑制剂， 利用二次冷 轧法制造生产的， 其主要生产工艺流程为- 冶炼→热轧—常化→一次冷轧→中间退火→二次冷轧→脱碳退火→高温 退火→绝缘涂层。 其中技术要点为- 冶炼： 用转炉 (或电炉)炼钢， 进行二次精炼及合金化， 连铸成板坯， 其 基本化学成分质量百分含量为 Si: 2.5〜4.5%, C: 0.02—0.10%, Mn: 0.025〜 0.25%, S或 Se: 0.01〜0.035%， Al^O.01%, ^O.005%, 有的成分体系还 含有 Cu、 Mo、 Sb、 B、 Bi等元素中的一种或多种， 其余为铁及不可避免的 杂质元素。
热轧： 一般将板坯在专用高温加热炉内加热到 1350°C以上的温度， 并进 行 45分钟以上的保温， 使有利的夹杂物 MnS或 MnSe充分固溶， 然后进行 4〜6道次的粗轧和精轧。逋过精轧和卷取之间的快速冷却， 可使碳化物弥散 分布在晶粒内， 有利于以后获得细小均匀的初次晶粒。
常化： 在 850〜950°C温度下保持 3分钟， 使热轧板组织更均匀。
一次冷轧： 冷轧压下率为 60〜70%， 经 3〜4道轧制。
中间退火： 中间退火温度为 850〜950°C， 退火时间为 2.5〜4.0分钟。 二次冷轧： 中间退火后的二次冷轧压下率为 50〜55%，冷轧道次为 2〜3 道。
脱碳退火： 通过脱碳退火完成初次再结晶并形成二次晶粒形核点。 将 C 含量脱至 30ppm以下，保证之后的高温退火时处于单一的 a相， 发展完善的 二次再结晶组织， 消除成品的磁时效。
确认本 高温退火： 必须先经高温退火进行二次再结晶并使二次晶粒长大， 然后 在带钢表面形成一层硅酸镁底层玻璃膜； 最后净化退火除掉抑制剂分解出来 的硫和氮等对磁性有害的元素，得到取向度高和理想磁性能的普通取向硅钢。
绝缘涂层： 经过涂布绝缘涂层和拉伸退火， 获得商业应用形态的取向硅 钢产品。
公开号为 CN1321787A, 公开日为 2001年 11月 14日， 名称为"单取向 电工钢板及其制备方法"的中国专利文献， 其公开了一种单取向电工钢板及 其制造方法。 该方法的制造工序包括: 将原材料进行冶炼， 其化学成分质量 百分含量为 C: 0.02—0.15%, Si: 1.5 2.5% Mn: 0.02—0.20%, 酸可溶性 的 Al; 0.015 0.065% N: 0.0030 0.0150%， 选自 S和 Se中的一种或两种 的总量： 0.005 0.040%， 余量为 Fe和不可避免的其他杂质； 在 900 1100 °C温度下进行热轧板卷退火，进行一次冷轧， 脱碳退火， 最终退火， 最后涂敷 后获得板厚为 0.20 0.55mm、 平均结晶粒径为 1.5 5.5mm的电工钢板， 其 铁损值 W17/50满足： Ο^δ^1.915^板厚 ^Wn/SOiW/kg^O SSe1'73 板厚
B8(T)值满足 1.88≤B8(T)^1.95
公开号为 US5039359, 公开日为 1991年 8月 13日， 名称为 "一种具有 优异磁性晶粒取向电工钢板的制造方法"的美国专利文献， 其涉及一种具有 优良磁性电工钢板的制造方法， 其制造方法的步骤为： 冶炼钢水， 其化学成 分的质量百分含量配比为 C: 0,021— 0.100 wt %, Si: 2.5—4.5 wt %, 其中 还含有硅钢板坯形成抑制剂， 其 铁和不可避免的其他杂质， 形成热轧卷取 钢板，卷取冷却温度 700°C，该温度比实际的热轧卷取钢板的温度降低 80% 以上， 在热轧钢板的工作表上组成的平衡一个或多个元素， 采取至少一次冷 轧生产取向硅钢， 该产品磁感^以达 1:90T以上。
公开号为 US5472521 , 公开日为 1995年 12月 5日， 名称为 "一种具有 优异磁性晶粒取向的电工钢板的制造 的美国专利文献， 其公开了一种 提高磁性和稳定晶粒取向的电工钢板的制造方法。其采用低温板坯加热技术、 免常化的一次冷轧工艺生产取向硅 ft， 同时还涉及了冶炼后氮含量与钢板磁 感的关系。
上述现有技术存在以下缺点：
( 1 )采用 MnS或 MnSe为主抑制剂， 导致成品磁性偏低； (2)为了使 MnS或 MnSe抑制剂充分固溶， 加热温度最高需达到 1400 °C， 这是传统加热炉的极限水平； 此外， 由于加热温度高、 烧损大， 加热炉 需频繁修补， 利用率低； 同时， 加热温度高导致能耗高， 热轧卷的边裂大， 致使冷轧工序生产困难， 成材率低， 成本也高；
(3 )在现有化学成分体系下，整个生产过程需要采用常化、中间退火以 及两次冷轧法才能获得磁性符合要求的普通取向硅钢成品， 从而导致工序繁 复、 制造工艺流程长， 生产效率过低；
(4)现有普通取向硅钢中的 MnS或 MnSe为完全固溶非氮化型， 其在 实际生成中由于板坯再加热温度过高， 会发生板坯内抑制剂强度不均匀， 易 生成粗大晶粒等， 这都会导致二次再结晶不完善， 磁感降低等问题。 发明内容
本发明的目的在于提供一种高磁感普通取向硅钢的制造方法， 采用该制 造方法能在省去常化、 中间退火等工序的前提下， 仅采用一次免时效轧制即 可获得较高磁感 (B8 ^ 1.88T)的普通取向硅钢。
为了实现上述发明目的， 本发明提供了一种高磁感普通取向硅钢的制造 方法， 其包括下列步骤： -
( 1 )冶炼、连铸后得到板坯，控制冶炼阶段的 N含量为 0.002〜0.014wt%;
(2) 热轧： 加热温度为 1090〜1200°C ;
(3 )冷轧： 一次免时效轧制；
(4) 脱碳退火；
(5)氮化处理：渗入氮含量 [N]D满足 328 - 0.14 a - 0.85 b - 2.33 c ^ [N]D ^ 362 - 0.16 a - 0.94 b - 2.57 c;其中， a为冶炼步骤 Als的含量，单位为 ppm; b为冶炼步骤 N元素的含量， 单位为 ppm; c为初次晶粒尺寸， 单位为 μ ιη;
(6)钢板表面涂覆氧化镁涂层， 进行退火；
(7)涂敷綠缘涂层。
发明人通过大量试验发现， 在炼钢过程中适当控制氮含量， 既能获得磁 感较高的产品， 又能免去常化和中间退火等工序， 并且将二次冷轧法转为一 次冷轧法， 使得生产周期缩短， 生产效率明显提高。 由于在本技术方案中， 脱碳退火工序后还需要采取氮化处理，因此需要在冶炼阶段可将 Ν含量控制 在较低范围内， 从而避免用高温来进行加热， 本技术方案中采用了 1090〜 1200°C的低温板坯加热技术进行生产制造。在本技术技术方案中， 当 N含量 不足 0.002%时，不能获得稳定的一次抑制剂效果，初次再结晶尺寸的控制变 得困难， 二次再结晶也不完善。 此时， 需要采用中间退火和二次冷轧工艺来 改善成品磁性。 然而， 当 N含量超过 0.014%时， 在实际的生产过程中既需 要使板坯再加热温度升至 1350°C以上， 又由于后工序的氮化处理， 会使高斯 取向度降低。另外， 当 N含量较高时，还需要增加常化工序来使得 A1N抑制 剂细小弥散的析出， 并采用一次冷轧时效轧制工艺来获得最终成品厚度的冷 轧板。 因此， 结合成品磁性， 生产效率及综合各项因素而言， 在本发明的技 术方案中， 需要将 N含量控制在 0.002〜0.014wt%。
本技术方案中的氮化处理是针对本技术方案中的低温板坯加热技术的， 其对冷轧脱碳板进行渗氮处理， 从而补充基板中不足抑制剂的强度， 所增加 的抑制剂是专门为进行二次再结晶所准备的二次抑制剂， 其数量的多少直接 决定了脱碳钢板在高温退火过程中二次再结晶的完善程度。 当氮化处理中的 渗入氮含量过少时， 会使抑制剂强度偏弱， 从而导致二次再结晶晶核位置扩 展到板厚方向， 不仅钢板近表层的尖锐高斯取向， 而且中心层的正常晶粒也 发生二次再结晶，致使取向度变差，磁特性劣化，使得成品的 B8降低。反之， 氮化处理中渗入氮含量过多时， 高斯取向度也会极为劣化， 并且在高温退火 过程中形成的硅酸镁玻璃膜上会发生露出金属缺陷， 且缺陷率会显著增加。 因此， 氮化处理的渗入氮含量应满足关系式： 328 - 0.14 a - 0.85 b - 2.33 c [N]D^362 - 0.16 a - 0.94 b - 2.57 c (a为冶炼步骤中 Als的含量， ppm; b为冶 炼步骤中 N元素的含量， ppm; c为初次晶粒尺寸， μ πι)。
进一步地， 在上述步骤 （2) 中， 1180°C以下开轧， 860°C以上终轧， 轧 后卷取， 卷取温度小于 650° ( 。
进一步地， 在上述步骤 （3 ) 中， 控制冷轧压下率 80%。
进一步地， 在上述步―骤 （4) 中， 控制升温速度 15〜35°C/s， 脱碳温度 800〜860°C， 脱碳露点 60〜70°C。
进一步地， 在上述步骤（4) 中保护气氛为 75%H2+25%N2 (体积分数）。 进一步地， 在上述步骤（5 ) 中， 采用体积分数为 0.5〜4.0%的 NH3进行 渗氮， 渗氮温度 760〜860°C， 渗氮时间 20〜50s， 氧化度 P¾O/PH2为 0.045〜 与现有技术相比， 本发明所述的高磁感普通取向硅钢的制造方法， 通过 控制冶炼过程中的 Ν含量， 并根据冶炼步骤中 Als的含量， N元素的含量和 初次晶粒尺寸控制后续过程中氮化处理的渗入氮含量， 在减少生产工艺流程 的前提下， 获得了磁感较高 (B8 1.88T)的普通取向硅钢， 不仅节省了生产工 序， 提高了生产效率， 而且还保证普通取向硅钢具备理想的磁性能和优良的 取向度。 具体实施方式
以下将结合具体实施例和比较例对本发明所述的技术方案作进一步的解 释说明。
实施例 1-3和比较例 1-2:
采用转炉或电炉炼钢， 钢水经二次精炼， 并在连铸后得到板坯， 其化学 元素质量百分数为： C: 0.02—0.08%, Si: 2.0〜3.5%， Mn: 0.05—0.20%, S: 0.005〜0.012%， Als: 0.010〜0.060%， N: 0.002〜0.014%， Sn: 0.10%， 余 量为 Fe及其他不可避免的杂质。 将不同成分的板坯放在 1150°C加热后热轧 至厚度为 2.3mm的热轧板， 开轧和终轧温度分别为 1070°C和 935°C， 卷取温 度 636°C。 热轧板经酸洗后， 一次冷轧到成品厚度 0.30mm。 脱碳退火升温速 率 25°C/s、 脱碳温度 845°C， 脱碳露点 67°C的条件下进行脱碳退火， 使钢板 中 [C]含量降到 30ppm 以下。 氮化处理工艺： 780X 30sec， 氧化度 P¾o/P¾ 是 0.065， ΝΉ3用量 3.2wt%， 渗入 [N]含量 160ppm。 涂布 MgO为主要成分的 隔离剂后， 在罩式炉中进行高温退火。 开卷后经过涂敷绝缘涂层及拉伸平整 退火， 得到的成品 和生产周期见表 1。
表 1. (余量为 Fe和其他不可避免的杂质， wt%)
序 C Si Mn S Als N Sn B8 热轧- -冷轧 工艺
号 (%) (%) (%) (%) (%) (%) (%) (T) 生产周期
1 0.04 2.0 0.10 0.012 0.03 0.014 0.04 1.90
3.5 免常化和中
2 0.06 0.20 0.005 0.06 0.008 0.10 1.88
间退火、 48小时
0.08 一次冷轧法
3 3.0 0.05 0.006 0.01 0.002 0.06 1.89
)
常化、 一次
4 0.05 3.2 0.15 0.006 0.03 0.016 0.06 1.85 48〜56小时 冷轧法 0.07 中间退火、
5 2.6 0.12 0.007 0.04 0.001 0.05 1.84 55-65小时 二次冷轧法
(序号 1-3分别为实施例 1-3， 序号 4-5分别为对比例 1-2 )
从表 1可以看出， 当 N元素含量控制在 0.002〜0.014%范围内时， 成品 的磁感普遍较高， 都能达到 B8 1.88T。 反之， 对比例 1-2的 N元素不满足 本发明所述的技术方案， 其磁感与实施例 1-3相比较稍低。
此外， 从表 1还可以看出， 当冶炼阶段的 N含量满足 0.002〜0.014%时， 可以免去常化和中间退火步骤， 同时采用一次冷轧工艺技术， 这就使得从热 轧板到最终成品冷轧板的生产周期控制在 48小时以内。 否则， 当 N含量不 满足要求时， 由于需要进行常化、 中间退火和二次冷轧等工序， 会将生产周 期延长约 5~20小时。 实施例 4-8和对比例 3-7:
采用转炉或电炉炼钢， 钢水经二次精炼， 并在连铸后得到板坯， 其化学 元素质量百分数为 Si: 3.0%， C: 0.05%, Mn: 0.11%, S: 0.007%, Als: 0.03%, N: 0.007%, Sn: 0.06%, 其余为 Fe及不可避免的杂质； 然后进行热轧， 不同 的热轧工艺条件如下表 2所示。热轧板经酸洗，一次冷 到成品厚度 0.30mm。 脱碳退火升温速率 25°C/s、 脱碳温度 840°C， 脱碳露点 70 °C的条件下进行脱 碳退火， 使钢板中 [C]含量降到 30ppm以下。 氮化处理工艺： 800°C x30sec， 氧化度 PH2O/P¾是 0.14， NH3用量 l .lwt%， 渗入 [N]含量 200ppm。 涂布 MgO 为主要成分的隔离剂后， 在罩式炉中进行高温退火。 开卷后经过涂敷绝缘涂 层及拉伸平整退火， 得到的成品 B8见表 2。
表 2
板坯加热温
开轧温度 终轧温度 卷取温度 Bg
序号 度
C) (。C) CC) (T)
CC)
实施例 4 1090°C 1060 945 576 1.88 实施例 5 1200°C 1070 880 628 1.89 实施例 6 1150°C 1180 940 564 1.89 实施例 7 1130°C 1050 860 550 1.88 实施例 8 1100。C 1065 930 650 1.90 对比例 3 1085 V 1090 905 625 1.83 对比例 4 1205 V 1054 885 589 1.85 对比例 5 1105°C 1185 936 640 1.85 对比例 6 1160°C 1081 850 580 1.84 对比例 7 1135°C 1140 920 660 1.84 从表 2 结果可以看到， 当热轧工艺满足： 板坯在加热炉内加热到 1090-1200 °C , 开轧温度 1180°C以下， 终轧温度为 860°C以上， 轧后层流冷 却， 650°C温度以下卷取时，实施例 4-8的磁感普遍更高,都能达到 B8 1.88T。 反之， 当热轧工艺与本技术方案不符时，对比例 3-7的磁感都较实施例偏低。 实施例 9-13和对比例 8-13 :
采用转炉或电炉炼钢， 钢水经二次精炼， 并在连铸后得到板坯， 其化学 元素质量百分数为 Si: 2.8%， C: 0.04%, S: 0.009%, Als: 0.04%, N: 0.005%, Mn: 0.10%, Sn: 0.03%, 其余为 Fe及不可避免的杂质。 将板坯在 1130°C下 加热， 而后热轧至厚度为 2.5mm的热轧板， 开轧和终轧温度分别为 1080°C 和 920°C， 卷取温度 605 C。 热轧板经酸洗， 冷轧到成品厚度 0.35mm， 然后 进行脱碳退火， 不同的脱碳退火工艺条件如下表 3所示。 脱碳退火后， 使钢 板中 [C]含量降到 30ppm以下。渗氮退火工艺： 800°C x30sec， 氧化度 PH2O/P¾ 是 0.15， NH3用量 0.9wt%, 渗入 [N]含量 170ppm。 涂布 MgO为主要成分的 隔离剂后， 在罩式炉中进行高温退火。 开卷后经过涂敷绝缘涂层及拉伸平整 退火， 得到的成品 B8见表 3。
表 3
Figure imgf000008_0001
从表 3可以看到， 当脱碳退火工艺满足: 脱碳升温速度 15~35°C/Sec， 脱 碳温度 800〜860°C， 脱碳露点 60~70°C时， 实施例 9-13的成品的磁感普遍更 高， 都能达到 B8 1.88T。 反之， 当脱碳退火工艺与本技术方案不符时， 对 比例 8-13的磁感都偏低 实施例 14-23和对比例 14-19:
采用转炉或电炉炼钢， 钢水经二次精炼， 并在连铸后得到板坯， 其化学 元素质量百分数为 Si: 3.0%， C: 0.05%, Mn: 0.11%, S: 0.007%, Als: 0.03%, N: 0.007%, Sn: 0.06%, 其余为 Fe及不可避免的杂质。 将板坯放在 1120 °C下 进行加热， 热轧至厚度为 2.5mm的热轧板， 开轧和终札温度分别为 1080°C 和 920°C， 卷取温度 605°C。 热轧板经酸洗， 冷轧到成品厚度 0.35mm。 而后 以升温速度 30°C/SeC， 脱碳温度 840°C， 脱碳露点 68 °C下进行脱碳退火。 然 后进行氮化处理， 不同的渗氮退火工艺条件如下表 4所示。 涂布 MgO为主 要成分的隔离剂后， 在罩式炉中进行高温退火。 开卷后经过涂敷绝缘涂层及 拉伸平整退火， 得到的成品 B8见表 4。
表 4
Figure imgf000009_0001
从表 4的试验结果可以看到， 当渗氮退火工艺满足本技术方案： 渗氮温 度 760〜860°C， 渗氮时间 20~50sec， 氧化度 P¾O/PH2 : 0.045-0.200 , NH3 :
0.5〜4.0wt%，渗入氮含量 328 - 0.14 a - 0.85 b - 2.33 c [N]D ^ 362 - 0.16 a - 0.94 b - 2.57 c时， 实施例 14-23的磁感普遍更高， 都能达到 B8 1.88T。 反 之， 当渗氮退火工艺与本技术方案不符时， 对比例 14-19的成品磁感都偏低。 实施例 24-29和对比例 20-25：
采用转炉^^电炉炼钢， 钢水经二次精炼， 并在连铸后得到板坯， 其化学 元素质量百分数为 Si: 2.8%, C: 0.045%, Mn: 0.06%, S: 0.009%, Als: 0.024%, N: 0.009%, Sn: 0.04%, 其余为 Fe及不可避免的杂质。 将板坯放在 1120 °C下 进行加热， 热轧至厚度为 2.3mm的热轧板， 开轧和终轧温度分别为 1070°C 和 900°C， 卷取温度 570°C。 热轧板经酸洗， 冷轧到成品厚度 0.30mm。 而后 以升温速度 20°C/Sec， 脱碳温度 830°C， 脱碳露点 70°C下进行脱碳退火。 然 后进行氮化处理， 不同的渗入氮含量对成品 B8的影响如下表 5所示。 涂布 MgO为主要成分的隔离剂后， 在罩式炉中进行高温退火。开卷后经过涂敷绝 缘涂层及拉伸平整退火， 得到的成 B8见表 5。
Figure imgf000010_0001
Figure imgf000010_0002
表 5反映了渗入氮含量对成品 的影响。从表 5可以看出，渗入氮含量 需要满足根据冶炼阶段 Als含量 a、N含量 b和初次晶粒尺寸 c理论计算得到 的渗入氮含量 [N]D (328 - 0.14 a - 0.85 b - 2.33 c ^ [N]D ^ 362 - 0.16 a - 0.94 b - 2.57 c)0 当实际渗氮量在计算值范围内时， 如实施例 24-29， 成品的磁感 较高； 反之， 如对比例 20-25， 其成品磁感偏低。 要注意的是， 以上列举的仅为本发明的具体实施例， 显然本发明不限于 以上实施例， 随之有着许多的类似变化。 本领域的技术人员如果从本发明公 开的内容直接导出或联想到的所有变形， 均应属于本发明的保护范围。

Claims

权 利 要 求 书
1. 一种高磁感普通取向硅钢的制造方法， 其特征在于， 包括下列步骤：
(1) 冶炼、 连铸后得到板坯， 控制冶炼阶段的 N含量为 0.002〜 0.014wt%;
(2)热轧： 加热温度为 1090〜1200°C;
(3)冷轧： 一次免时效轧制；
(4)脱碳退火；
(5)氮化处理： 渗入氮含量 [N]D满足 328 -0.14 a -0.85 b -2.33 c [ ]D ^ 362 -0.16a- 0.94 b - 2.57 c;其中， a为冶炼步骤 Als的含量， ppm; b为冶炼步骤 N元素的含量， ppm; c为初次晶粒尺寸， μπι;
(6)钢板表面涂覆氧化镁涂层， 进行退火；
(7)涂敷绝缘涂层。
2. 如权利要求 1所述的高磁感普通取向硅钢的制造方法，其特征在于，所述 步骤（2)中， 1180°C以下开轧， 860°C以上终轧， 轧后卷取， 卷取温度小 于 650°C。
3. 如权利要求 2所述的高磁感普通取向硅钢的制造方法，其特征在于，所述 步骤 （3) 中， 冷轧压下率 80%。
4. 如权利要求 3所述的高磁感普通取向硅钢的制造方法，其特征在于，所述 步骤（4)中，升温速度 15〜35°C/s，脱碳温度 800〜860°C，脱碳露点 60〜 70°C。
5. 如权利要求 4所述的高磁感普通取向硅钢的制造方法，其特征在于，所述 步骤 （4) 中保护气氛为 75%¾+25%N2。
6. 如权利要求 1-5中任意一项所述的高磁感普通取向硅钢的制造方法，其特 征在于， 所述步骤（5) 中， 采用体积分数为 0.5〜4.0%的 NH3进行渗氮， 渗氮温度 760〜860°C，渗氮时间 20〜50s，氧化度？ 0/?¾为 0.045〜0.200。
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JP2016156070A (ja) * 2015-02-25 2016-09-01 Ｊｆｅスチール株式会社 方向性電磁鋼板の製造方法
JP2016156069A (ja) * 2015-02-25 2016-09-01 Ｊｆｅスチール株式会社 方向性電磁鋼板の製造方法
CN110551968A (zh) * 2018-06-04 2019-12-10 武汉尚瑞科技有限公司 一种高磁感取向硅钢渗氮退火的生产方法及其产品
CN115502072A (zh) * 2022-10-26 2022-12-23 内蒙古工业大学 一种取向硅钢表面氧化镁涂覆方法
CN115502072B (zh) * 2022-10-26 2023-08-22 内蒙古工业大学 一种取向硅钢表面氧化镁涂覆方法

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EP2902507B1 (en) 2018-11-28
CN103695619A (zh) 2014-04-02
RU2609605C2 (ru) 2017-02-02
MX366340B (es) 2019-07-05
CN103695619B (zh) 2016-02-24
JP2015537112A (ja) 2015-12-24
US9905361B2 (en) 2018-02-27
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JP6461798B2 (ja) 2019-01-30
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