CN101730752B - 对ahss或者uhss带材进行热浸镀锌的方法以及所得带材 - Google Patents
对ahss或者uhss带材进行热浸镀锌的方法以及所得带材 Download PDFInfo
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- 238000005246 galvanizing Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title abstract description 11
- 229910000937 TWIP steel Inorganic materials 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910000885 Dual-phase steel Inorganic materials 0.000 claims abstract 4
- 229910000831 Steel Inorganic materials 0.000 claims description 42
- 239000010959 steel Substances 0.000 claims description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000005097 cold rolling Methods 0.000 claims description 9
- 208000037656 Respiratory Sounds Diseases 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009749 continuous casting Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 3
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 abstract description 6
- 229910000794 TRIP steel Inorganic materials 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002436 steel type Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/06—Zinc or cadmium or alloys based thereon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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Abstract
本发明涉及一种对先进的高强度或者超高强度钢带材,例如双相钢、相变诱发塑性钢、相变诱发塑性辅助双相钢以及孪生诱发塑性钢带材进行热浸镀锌的方法。依据本发明,在对带材进行热浸镀锌之前,对带材进行酸洗并随后加热到低于连续退火温度的温度。
Description
技术领域
本发明涉及一种对先进高强度或者超高强度钢带材进行热浸镀锌的方法。
背景技术
先进高强度钢(AHSS)和超高强度钢(UHSS)通常用于下述钢类型,即所述钢类型比普通的C-Mn钢和高强度钢具有更高的屈服强度。AHSS的屈服强度超过400MPa,UHSS的屈服强度超过600MPa。为了阅读的方便,在本说明书中,AHSS和UHSS合起来由AHSS表示。
特别地,为汽车工业而开发了AHSS类型。AHSS类型是例如双相(DP)钢、相变诱发塑性(TRIP)钢、TRIP辅助双相(TADP)钢和孪生诱发塑性(TWIP)钢。通常,这些钢类型在其缩写之后具有表示屈服强度的数字,例如DP600和TRIP700。AHSS类型中的一些已经处于生产,而其它的正在开发。
对于大多数的汽车应用,要求AHSS带材覆盖有锌层(所述锌层有时候包含至多几个百分比的其它元素)。然而,本领域内公知的是,AHSS类型难以利用热浸镀锌来覆盖锌层,并且已经发现对于含有大量合金化元素的AHSS(例如TWIP钢)尤为如此。依据现有技术水平,这些AHSS类型的热浸镀锌会在覆锌的AHSS材料变形期间导致裸点(bare spot)、锌层剥落、以及在锌层中形成裂纹。
发明内容
本发明的一个目的是提供一种用于AHSS钢带材热浸镀锌的改良方法。
本发明的另一目的是提供一种用于AHSS带材热浸镀锌的方法,通过该方法减少或消除了裸点的形成和锌层的剥落,以及减少或消除了在AHSS带材变形期间锌层中裂纹的形成。
此外,本发明的一个目的是提供这样的热浸镀锌AHSS带材。
根据本发明,利用一种对先进高强度或者超高强度钢带材进行热浸镀锌的方法实现了一个或多个这些目的,该钢带材为例如DP钢,TRIP钢,TRIP辅助DP钢以及TWIP钢的带材,其中在对带材热浸镀锌之前对所述带材进行酸洗并随后加热到低于连续退火温度的温度。
用这种方法,该AHSS带材仅被加热到高至足以形成封闭的抑制层的温度。该温度低于因冶金学因素(例如再结晶从而影响机械性能)所必需的常规连续退火温度。由于该AHSS带材被加热到低于常规连续退火温度的温度,因此可以减少该钢带材表面上的氧化物形成。
优选地,该低于连续退火温度的温度在400到600℃之间。在该温度范围内,氧化物的形成显著减少,并且带材被充分加热以便进行随后的热浸镀锌。
依据优选的实施方案,在加热到低于连续退火温度的温度期间或之后并且在热浸镀锌之前该带材中的Fe被还原。通过还原该带材,形成的Fe氧化物被还原,并且以这种方式,热浸镀锌之前在该带材表面上存在的氧化物量显著降低。
优选地,采用H2N2来实施还原,更优选地,在还原气氛中使用5-30%的H2N2。已经发现通过使用该气氛,可以去除大多数的氧化物。
依据优选的实施方案,在带材的加热期间或之后并且在带材的还原之前,在气氛中提供过量的O2。提供过量的氧气可以改善钢带材在热浸镀锌之前的表面品质,从而改善涂覆在AHSS带材上的锌层的品质。据认为氧会在AHSS带材的表面和内部与该带材中的合金化元素结合,并且以这种方式,形成的氧化物不能迁移到带材的表面。氧化之后的还原性气氛这时将还原带材表面的氧化物,并且以这种方式,带材表面的氧化物量显著减少或甚至几乎不存在,如实验所示。
优选地,以0.05-5% O2的量提供过量的O2。发现该氧气量是足够的。
依据第一优选实施方案,该钢带材作为热轧带材进行热浸镀锌。因此,可对热轧的AHSS带材进行热浸镀锌,而不管该带材采用何种方式生产,如通过半连铸生产。
优选地,对热轧带材进行热浸镀锌,而不在该带材的热轧和热浸镀锌之间进行连续退火步骤。依据本发明的方法,不需要这样的连续退火步骤,从而可以实现显著的费用节省。
依据第二优选实施方案,该钢带材作为冷轧产品进行热浸镀锌,该冷轧产品在冷轧后和酸洗前被退火。以这种方式提供适合于汽车工业的冷轧热浸镀锌AHSS带材。
优选地,在冷轧前对钢带材进行酸洗。冷轧前的酸洗(常常)是必要的以便去除氧化物,从而防止氧化物的轧入。
优选地,冷轧带材由热轧带材或者带式连铸带材制成。特别地,对于AHSS带材,需要选择合适的铸造和热轧方法。
因此可以清楚,对冷轧AHSS材料采用本发明的方法,在冷轧步骤之前和之后都要实施酸洗。
依据优选的实施方案,该先进高强度或者超高强度钢带材包含0.04-0.30%C,1.0-3.5% Mn,0-1.0% Si,0-2.0% Al和0-1.0%Cr。可以存在其它元素,例如V,Nb,Ti和B,但是通常以少量存在。
优选地,该钢带材为相变诱发塑性钢带材,包含0.15-0.30%C、1.5-3.5%Mn、0.2-0.8%Si和0.5-2.0%Al,优选0.15-0.24%C、1.5-2.0%Mn、0.2-0.6%Si和0.5-1.55Al。也可以存在少量的其它合金化元素。
依据上述所有实施方案中的优选实施方案,该钢带材为TWIP钢带材,包含10-40%锰,优选12-25%锰,和至多10%铝。TWIP钢带材非常难以适当地镀锌,然而对于具有上述锰含量的TWIP钢带材而言,依据本发明的方法被证实是合适的。
依据本发明的第二方面,提供了一种根据前述制备的先进高强度或超高强度钢带材,在该钢带材上包含热浸镀锌的锌层,在变形期间所述锌层基本上不产生裸点、剥落或裂纹,该AHSS带材非常适用于汽车工业。
优选地,在该钢带材和锌层之间基本上不存在氧化物。由于不存在氧化物,锌层非常良好地附着于该AHSS带材。
优选地,该AHSS带材为TWIP钢带材,该TWIP钢带材含有10-40%锰,在该钢带材上包含热浸镀锌的锌层,在变形期间所述锌层基本上不产生裸点、剥落或裂纹。
附图说明
将参照附图以实施例来描述本发明:
图1示出依据现有技术的镀锌TWIP带材的横截面中存在的氧化物。
图2示出依据本发明制备的镀锌TWIP带材的横截面中存在的氧化物。
具体实施方式
依据实施例,TWIP钢带材含有14.8%Mn和3%Al作为合金化元素。在热轧、酸洗和冷轧之后,该TWIP钢带材被连续退火至约800℃的温度并再次进行酸洗。然后该带材在退火线中被加热到527℃的温度,随后在约450℃的镀锌浴中进行热浸镀锌。
在加热该带材至527℃的温度期间,提供1%过量的O2。在如此高温下提供氧气(stat)不仅在带材表面形成氧化物,还在表面下方的一些深度处与合金化元素结合。
在提供氧气之后,使用约5% H2N2还原该带材。该带材的还原从表面去除了氧化物,然而在表面下方形成的氧化物保留在原处并且不能迁移到表面。因此,通过还原表面,氧化物被有效地去除并且不能在表面上形成新的氧化物。
据认为通过普通的还原,在合金化温度下在AHSS类型中大量存在的合金化元素会非常快速的迁移到表面,因此进行热浸镀锌前会在表面再次形成氧化物。
不管确切的机制是什么,已发现利用本发明的方法可以明显减少或几乎消除存在于TWIP钢上的热浸镀锌的锌层中的氧化物量。图1示出了在依据现有技术的此类层的横截面中存在的氧化物。在横轴上给出了在锌层表面下方的距离,在纵轴上给出了氧化物和锌的量(在图1和图2中)。从图1中可以清楚,在从钢基体到锌覆层的过渡区中存在许多氧化物,这些氧化物引起锌层与基材的不良附着,从而在弯曲该材料时在锌层中导致裸点、剥落和形成裂纹。图2示出了依据本发明制备的镀锌TWIP带材的横截面中存在的氧化物。氧化物(几乎)不再出现,并且与依据现有技术进行热浸镀锌的材料相比,依据本发明的热浸镀锌的TWIP钢带材在关于裸点、剥落和裂纹方面具有好得多的性能。
Claims (17)
1.对双相钢、相变诱发塑性钢、相变诱发塑性辅助双相钢或者孪生诱发塑性钢带材进行热浸镀锌的方法,其特征在于,在对该带材进行热浸镀锌之前,对该带材进行酸洗并随后加热到低于连续退火温度的温度,该低于连续退火温度的温度在400到600℃之间,
其中在加热到低于连续退火温度的温度期间或之后并且在热浸镀锌之前将带材中的Fe还原,并且其中在加热带材期间或之后并且在带材还原之前,在气氛中提供过量的O2。
2.根据权利要求1的方法,其中在还原气氛中采用H2N2来实施所述还原。
3.根据权利要求2的方法,其中在还原气氛中使用5-30%的H2N2来实施所述还原。
4.根据权利要求1的方法,其中以0.05-5%O2的量提供过量的O2。
5.根据权利要求1的方法,其中该钢带材作为热轧带材进行热浸镀锌。
6.根据权利要求5的方法,其中对该热轧带材进行热浸镀锌,在该带材的热轧和热浸镀锌之间没有连续退火步骤。
7.根据权利要求1的方法,其中该钢带材作为冷轧产品进行热浸镀锌,在冷轧之后并且在酸洗之前对其进行退火。
8.根据权利要求7的方法,其中该钢带材在冷轧之前经历酸洗。
9.根据权利要求7的方法,其中该冷轧带材由热轧带材或者带式连铸带材制成。
10.根据权利要求1的方法,其中该钢带材包含0.04-0.30%C,1.0-3.5%Mn,0-1.0%Si,0-2.0%Al和0-1.0%Cr,余量为Fe以及不可避免的杂质。
11.根据权利要求1的方法,其中该钢带材为相变诱发塑性钢带材,包含0.15-0.30%C,1.5-3.5%Mn,0.2-0.8%Si和0.5-2.0%Al,余量为Fe以及不可避免的杂质。
12.根据权利要求11的方法,其中该钢带材为相变诱发塑性钢带材,包含0.15-0.24%C,1.5-2.0%Mn,0.2-0.6%Si和0.5-1.5%Al,余量为Fe以及不可避免的杂质。
13.根据权利要求1的方法,其中该钢带材为孪生诱发塑性钢带材,包含10-40%锰和至多10%铝。
14.根据权利要求13的方法,其中该钢带材为孪生诱发塑性钢带材,包含12-25%锰和至多10%铝。
15.根据权利要求1-13或14中任一项的方法制备的钢带材,在该钢带材上包含热浸镀锌的锌层,在变形期间所述锌层基本上没有裸点、剥落或裂纹。
16.根据权利要求15的钢带材,其中在该钢带材和锌层之间基本上不存在氧化物。
17.根据权利要求13的方法制造的孪生诱发塑性钢带材,含有10-40%锰,在该钢带材上包含热浸镀锌的锌层,在变形期间所述锌层基本上没有裸点、剥落或裂纹。
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PCT/EP2008/055209 WO2008135445A1 (en) | 2007-05-02 | 2008-04-29 | Method for hot dip galvanising of ahss or uhss strip material, and such material |
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CN104169027A (zh) * | 2012-04-03 | 2014-11-26 | 日立金属株式会社 | Fe-Al系合金的制造方法 |
BR112019018170B1 (pt) * | 2017-03-03 | 2023-10-31 | Utica Enterprises, Inc | Método para prender uma porca rebitada em uma chapa de ahss e montagem |
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