CN117561348A - 炉内结构物的被覆材料和表面被覆方法以及炉内结构物 - Google Patents
炉内结构物的被覆材料和表面被覆方法以及炉内结构物 Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 30
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000003466 welding Methods 0.000 claims abstract description 9
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- 239000007921 spray Substances 0.000 claims abstract 2
- 238000007789 sealing Methods 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 61
- 230000007797 corrosion Effects 0.000 abstract description 60
- 239000011651 chromium Substances 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 15
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- 229910052804 chromium Inorganic materials 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
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- 150000004770 chalcogenides Chemical class 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 238000005486 sulfidation Methods 0.000 description 5
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
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- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- -1 Mo and S is high Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- C—CHEMISTRY; METALLURGY
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- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3046—Co as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- 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
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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- C23C4/123—Spraying molten metal
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract
本发明提供耐硫族腐蚀性优良的炉内结构物的被覆材料和表面被覆方法以及炉内结构物。一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物的被覆材料,其中,材料成分组成以质量基准计含有Co:45%以上且72%以下、Mo:20%以上且35%以下、Cr:8%以上且25%以下和Si:0.1%以上且5%以下,实质上不含Ni。一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物的表面被覆方法,其中,通过堆焊或喷镀在炉内结构物的表面形成上述被覆材料。一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物,其中,在表面形成有使用上述被覆材料而成的覆膜。
Description
技术领域
本发明涉及配置在含有硫、硒和碲中的任一种硫族元素的高温腐蚀气氛下的炉内结构物、对该炉内结构物赋予优良的耐腐蚀性的被覆材料和其表面被覆方法。
特别是还涉及在进行钢板的退火的退火炉中输送钢板的炉底辊表面上的被覆材料。
背景技术
通常,被称为高温腐蚀的加速损耗现象在其气氛或接触物中含有硫、硒和碲中的任一种硫族元素的化合物的情况下作为硫化腐蚀而已知,在使用比较高温的燃烧气体的加热炉中经历过。在含有这样的硫族元素的高温腐蚀环境下的炉内结构物中,产生因硫化腐蚀引起的设备损耗。
专利文献1中公开了如下技术:对炉内结构物实施含铬碳化物的金属陶瓷或铬碳化物与自熔性合金、哈氏合金或因科镍(Inconel)合金等Ni基合金的喷镀,对炉内结构物赋予耐硫酸腐蚀性作为耐磨损性和耐酸性。
另外,在炼铁工艺中用于输送钢板的炉底辊由于长时间连续地使用,因此发生炉内浮游物和钢板上的氧化物或铁粉凝结沉积在炉底辊的表面的、被称为所谓堆积(buildup)的不良。作为其对策,专利文献2中公开了如下技术:通过对炉底辊表面喷镀含有Co和Al并且包含选自Cr、Ni、C、Ta、Y、Mo和Zr中的一种或两种以上的喷镀材料来进行表面改性,使其具备耐堆积性。
现有技术文献
专利文献
专利文献1:日本特开平9-75832号公报
专利文献2:日本特开昭60-141861号公报
发明内容
发明所要解决的问题
但是,上述现有技术存在如下问题。即,在含有硫、硒和碲中的任一种硫族元素的高温腐蚀气氛下的炉内,对作为炉内结构物的耐热钢和耐热/耐腐蚀合金实施喷镀来提高耐腐蚀性。但是,存在如下问题:无法消除这些硫族元素所引起的硫化腐蚀,炉内结构物损耗,设备的寿命变短,并且导致保养费用的增加。
本发明人阐明了硫族元素所引起的腐蚀现象的机理,在此基础上,本发明的目的在于,提供解决了这些上述问题的耐硫族腐蚀性优良的炉内结构物的被覆材料,提出该被覆材料向炉内结构物的表面被覆方法,进而提供具备耐高温腐蚀性的炉内结构物。
用于解决问题的方法
本发明为了解决上述问题,通过使合金设计最优化,发现了耐硫族腐蚀性优良的防腐蚀材料。即,本发明中,第一方式提供一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物的被覆材料,其特征在于,材料成分组成以质量基准计含有Co:45%以上且72%以下、Mo:20%以上且35%以下、Cr:8%以上且25%以下、Si:0.1%以上且5%以下,实质上不含Ni。
需要说明的是,另外,对于如上所述构成的本发明的炉内结构物的被覆材料而言,以下方式可成为更优选的解决手段:材料成分组成以质量基准计还含有选自Al:8.0%以下、Y:1.5%以下、Ta:7.0%以下、Mg:2.0%以下和W:8.0%以下中的至少一种。
另外,本发明中,第二方式提出一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物的表面被覆方法,其特征在于,使用上述被覆材料,通过堆焊或喷镀在炉内结构物的表面形成覆膜。
另外,本发明中,第三方式提供一种在含有硫族元素的高温腐蚀环境中使用的炉内结构物,其特征在于,在表面形成有使用上述被覆材料而成的覆膜。
需要说明的是,另外,对于如上所述构成的本发明的炉内结构物而言,以下方式等可成为更优选的解决手段:
a.上述覆膜通过喷镀法形成,利用无机类封孔剂将覆膜的气孔密封;
b.上述炉内结构物为退火炉内辊。
发明效果
根据本发明,对于在含有硫族元素的高温腐蚀环境中使用的炉内结构物,形成由被覆材料构成的覆膜,该被覆材料由以Co作为主要成分、含有规定量的Mo和Cr且实质上不含Ni的成分组成构成,由此能够提高耐硫族腐蚀性,即,能够防止因共晶反应引起的高温腐蚀,能够提高炉内结构物的耐用年数。
特别是由于不发生高温腐蚀,因此能够长期地维持输送钢板的退火炉内辊的表面的平滑性、稳定性,还具有防止被输送的钢板表面品质的降低的效果。
除此以外,本发明通过喷镀法在炉内结构物的表面形成由上述被覆材料构成的覆膜,对该覆膜的表面实施无机类封孔处理,由此将在覆膜中形成的气孔封孔,并且能够在表面形成保护氧化覆膜,还具有能够获得耐硫族腐蚀性的进一步提高的效果。
附图说明
图1是示出炉内结构物因高温的硫化腐蚀而损耗进行的情形的放大照片,(a)是初始状态的表层截面SEM照片,(b)是示出表面粗糙的表层截面SEM照片,(c)是示出腐蚀的进行的表层截面SEM照片,(d)是示出覆膜的损耗的表层截面SEM照片,(e)是示出S向覆膜的侵入、反应状况的表层截面的S分析结果映射图,(f)是示出实机中的损耗状况的结构物表面SEM照片。
图2是示出模拟了硫化腐蚀的高温腐蚀试验方法的概念图,(a)示出样品形状和腐蚀灰涂布状况,(b)示出加热模式。
图3是示出封孔处理的效果的高温腐蚀试验后的试验片表层截面照片,(a1)示出未实施封孔处理的样品的SEM图像,(a2)示出其O分析映射图,(a3)示出其Si分析映射图,(a4)示出其Cr分析映射图,(b1)示出实施了封孔处理的样品的SEM图像,(b2)示出其O分析映射图,(b3)示出其Si分析映射图,(b4)示出Cr分析映射图。
图4是在高温腐蚀环境下使用的辊的表层截面SEM照片,(a1)示出现有例的使用前,(a2)示出现有例的使用后,(b1)示出发明例的使用前,(b2)示出发明例的使用后。
具体实施方式
<硫族元素所引起的腐蚀机理>
本发明人认为,硫族元素所引起的高温腐蚀现象基于如下所述的机理。
(1)通过在耐热钢或耐热-耐腐蚀合金表面形成的保护氧化覆膜,大致具备高温环境下的耐腐蚀性。但是,由于使用期间中的与气氛的反应,保护氧化覆膜生长、厚膜化,由此覆膜内部应力增大。与此相伴,发生部分剥离,产生保护氧化覆膜的缺损。除此以外,由于与输送物等的机械接触,因磨损等而产生保护氧化覆膜的缺损。
(2)保护氧化覆膜缺损后,在材料表面存在覆膜中所含的Al、Cr等元素的期间,可进行保护氧化覆膜的再生。但是,会发生某种形成保护氧化覆膜的元素的缺乏。
(3)由于保护氧化覆膜消失、即形成保护氧化覆膜的元素缺乏,导致作为耐热钢或耐热-耐腐蚀合金中的基础金属成分的Ni、Co、Fe等与硫族元素发生反应。
(4)由于发生硫族元素与这些合金中的基础金属成分的共晶反应,材料熔融,导致损耗。
将导致保护覆膜的损耗的形态变化和硫族元素所引起的腐蚀状况示于图1中。图1的炉内结构物是退火炉的输送辊,其在含有硫族化合物的700℃以上的气氛下使用。图1(a)是炉内结构物的初始状态的表层截面SEM照片,在母材1表面以约200μm的厚度形成有覆膜2。该覆膜2是通过喷镀法使CoNiCrAlYTaSi的耐热合金堆积而成的。图1(b)示出由于720小时的使用而开始产生表面粗糙的时刻的炉内结构物的表层截面SEM照片。图1(c)是示出由于2160小时的使用而导致的腐蚀的进行状况的炉内结构物的表层截面SEM照片。在覆膜2的约一半的厚度观察到腐蚀。图1(d)是示出由于2880小时的使用而覆膜2的一部分剥离、腐蚀进行至母材1的状况的炉内结构物的表层截面SEM照片。图1(e)是与图1(d)相同视野的S分析结果映射图,明确了S向覆膜2的侵入状况以及母材1与S的共晶反应的情形。
基于如上所述的硫族元素所引起的高温腐蚀机理的理解,对炉内结构物的被覆材料的成分设计进行了研究。首先,在含有硫族元素的高温腐蚀气氛下的炉内结构物中,使用耐热合金作为表面被覆材料,但是,如上所述,由于合金中的Ni、Co与S等硫族元素的共晶反应而使得熔点降低,因此导致腐蚀进行。
特别是,Ni-S系的共晶温度为645℃,因此将不含Ni作为成分设计的基础。另一方面,发现Cr、Mo与S等硫族元素生成高熔点的化合物,因此,高温稳定性提高,有助于耐腐蚀性,并且发现通过制成含有适量Cr和Mo的Co基合金,耐硫族腐蚀性显著提高。除此以外,在本发明中,在通过喷镀法在炉内结构物的表面形成覆膜的情况下,通过进一步对表面实施无机类封孔处理,能够进一步提高耐硫族腐蚀性,能够延长炉内结构物的耐用年数。
以下,对作为本发明的第一实施方式的炉内结构物的被覆材料的成分组成进行说明。在以下的化学组成中,只要没有特别说明,则“%”表示“质量%”。
Co:45%以上且72%以下
在本发明中,从被覆合金中排除与硫族元素的共晶点低的Ni,将Co作为主要成分,因此,不形成因共晶反应引起的熔融物,能够得到优良的耐硫族腐蚀性。Co是本发明的被覆材料的主要构成元素,以45%以上且72%以下的范围含有。Co小于45%时,不能得到充分的耐腐蚀性,另一方面,超过72%时,不能得到后述的Mo、Cr的耐腐蚀性改善效果,因此Co的含量设定为45%以上且72%以下的范围。优选为48%以上且65%以下的范围。
Mo:20%以上且35%以下
Mo与S等硫族元素的化合物的熔点高,使Co基合金的高温耐腐蚀性提高。Mo小于20%时,有可能Co与硫族元素发生共晶反应。因此,Mo有助于Co的耐腐蚀性强化,实现共晶点升高,因此Mo需要为20%以上。另一方面,Mo超过35%时,Co的含有比率降低,反而有可能使耐腐蚀性降低,因此将上限设定为35%。优选为25%以上且30%以下的范围。
Cr:8%以上且25%以下
Cr与O、S等硫族元素的化合物的熔点高,使Co基合金的高温耐腐蚀性提高。Cr小于8%时,由于高温气氛中的氧引起的高温氧化反应而发生损耗,因此设定为8%以上。另一方面,即使含有超过25%,上述效果也饱和,而且反而Co的含量降低,耐腐蚀性有可能降低,因此将上限设定为25%。优选为8%以上且20%以下的范围。
Si:0.1%以上且5%以下
Si生成Mo硅化物,高温硬度提高,并且与Cr同样具有防止Co基合金的腐蚀性的效果,可以添加至5%。为了得到上述效果,需要含有0.1%以上,优选含有2.5%以上。
Ni:实质上不含
如上所述,Ni与S等硫族元素的共晶化合物的熔点低,有可能使在700℃以上的气氛下使用的炉内结构物的硫化腐蚀进行,因此设定为实质上不含。“实质上不含”是指不主动地添加Ni,并不排除作为不可避免的杂质的Ni。
除上述以外,作为使耐腐蚀性、覆膜的耐剥离性提高的元素,可以含有选自Al:8.0%以下、Y:1.5%以下、Ta:7.0%以下、Mg:2.0%以下和W:8.0%以下中的至少一种。
Al即使含有超过8.0%,反而其他有效元素的含量降低,耐腐蚀性也有可能降低,因此将上限设定为8.0%。
Y使Cr、Al、Si等的表面氧化物的耐剥离性提高,但即使含有超过1.5%,效果也饱和,因此将上限设定为1.5%。
Ta含有超过7.0%时,形成Ta氧化物,耐腐蚀性降低,因此将上限设定为7.0%。
Mg含有超过2.0%时,生成低熔点化合物,因此将上限设定为2.0%。
W使覆膜的高温硬度提高,并且有助于耐腐蚀性提高,但含有超过8.0%时,形成W氧化物,耐腐蚀性降低,因此将上限设定为8.0%。
接着,本发明的第二实施方式是使用上述成分组成的被覆材料在炉内结构物的表面形成覆膜的方法。作为其方法,可以例示堆焊、喷镀法。优选通过激光焊接或PTA焊接(等离子转移弧堆焊,Plasma Transferred Arc welding)等堆焊或者等离子喷镀或HVOF(高速氧燃料,High Velocity Oxy-Fuel)喷镀、爆炸喷镀等喷镀进行被覆。特别是在将本发明的被覆材料通过喷镀法进行制膜的情况下,在喷镀覆膜形成有气孔。由于硫族元素从该气孔侵入覆膜内而可能发生母材合金的腐蚀,因此,通过进一步利用无机类封孔剂对该覆膜实施封孔处理,能够防止腐蚀成分向气孔内的侵入,能够得到上述覆膜的耐硫族腐蚀性的进一步提高。
此外,本发明的第三实施方式是在表面形成有上述覆膜的炉内结构物。特别是在通过喷镀法形成覆膜的情况下,优选利用无机类封孔剂使气孔密封。作为无机类封孔剂,可以例示生成金属氧化物的铬酸类、金属醇盐醇类、硅酸盐类等。特别优选硅酸盐类的无机类封孔剂。另外,作为炉内结构物,优选应用于退火炉内辊,在耐堆积性的方面而言使用效果也大。已知退火炉内在燃烧气体中含有大量硫族元素的化合物。
实施例
<实施例1>
母材使用24Cr-12Ni钢(SCH13),制作通过喷镀法形成有由表1的成分组成的被覆材料构成的覆膜的试验片,供于图2所示的高温腐蚀试验。无机封孔处理使用硅酸盐类的无机类封孔剂。图2(a)所示的样品形状设为25mm见方×20mm厚度,将硫酸钠(Na2SO4)540mg作为腐蚀灰涂布在样品表面的10mm见方的范围。将该样品按照图2(b)所示的温度模式进行加热。覆膜的残留率由腐蚀试验前后的样品截面SEM图像中的覆膜的厚度以百分率的形式求出,将结果一并记于表1中。
对于样品No.1-4和No.11-16而言,被覆材料的成分组成在本发明的范围内,在腐蚀试验后残留了充分的覆膜残留厚度。对于含有Ni的样品No.7-10而言,在腐蚀试验后覆膜发生损耗,母材腐蚀。对于Co、Cr或Mo不满足本发明的范围的样品No.5、No.6和No.17而言,在腐蚀试验后没有得到充分的覆膜残留厚度。对于样品No.1-4而言,可知即使被覆材料的成分组成相同,但通过实施无机封孔处理,耐腐蚀性也提高,覆膜残留率为高位。
<实施例2>
对于表1的样品No.1和No.3,在图3中示出基于封孔处理的有无的高温腐蚀试验后的样品表层截面的SEM图像和分析结果。图3(a1)~(a4)分别示出未实施封孔处理的情况下的、表层截面SEM照片、O分析映射图、Si分析映射图和Cr分析映射图。在无封孔处理的情况下,在覆膜表面形成了大量Cr2O3。图3(b1)~(b4)分别示出实施了封孔处理的情况下的、表层截面SEM照片、O分析映射图、Si分析映射图和Cr分析映射图。在有封孔处理的情况下,在覆膜表面形成了大量SiO2,未形成Cr2O3。即,在任一种情况下,通过在表面形成氧化膜都能够防止S的侵入,但来自初期覆膜的成分变化更少的是实施了封孔处理的情况,由于表面性状得到了维持,因此也可以说在应用于实机时更优选实施了封孔处理。
<实施例3>
将本发明应用于实机退火炉的辊中。将样品No.3(发明例)的被覆材料和样品No.10(现有例)的被覆材料等离子喷镀到退火炉的炉底辊的表面上,在图4中分别示出使用4320小时后的表层截面SEM照片。可知:在现有例中,在使用后几乎不残留覆膜,另一方面,在发明例中,覆膜几乎未损耗。
产业上的可利用性
认为本发明的被覆材料、表面被覆方法和炉内结构物中提出的技术例如也可以在其他一般的高温腐蚀环境的领域中展开。
符号说明
1 母材
2 覆膜
3 样品
4 腐蚀灰涂布区域
Claims (6)
1.一种炉内结构物的被覆材料,其是在含有硫族元素的高温腐蚀环境中使用的炉内结构物的被覆材料,其中,材料成分组成以质量基准计含有Co:45%以上且72%以下、Mo:20%以上且35%以下、Cr:8%以上且25%以下、Si:0.1%以上且5%以下,实质上不含Ni。
2.根据权利要求1所述的炉内结构物的被覆材料,其中,材料成分组成以质量基准计还含有选自Al:8.0%以下、Y:1.5%以下、Ta:7.0%以下、Mg:2.0%以下和W:8.0%以下中的至少一种。
3.一种炉内结构物的表面被覆方法,其是在含有硫族元素的高温腐蚀环境中使用的炉内结构物的表面被覆方法,其中,使用权利要求1或2所述的炉内结构物的被覆材料,通过堆焊或喷镀在炉内结构物的表面形成覆膜。
4.一种炉内结构物,其是在含有硫族元素的高温腐蚀环境中使用的炉内结构物,其中,在表面形成有使用权利要求1或2所述的炉内结构物的被覆材料而成的覆膜。
5.根据权利要求4所述的炉内结构物,其中,所述覆膜通过喷镀法形成,利用无机类封孔剂将覆膜的气孔密封。
6.根据权利要求4或5所述的炉内结构物,其中,所述炉内结构物为退火炉内辊。
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JP4229508B2 (ja) * | 1999-01-29 | 2009-02-25 | 第一高周波工業株式会社 | 高温ハースローラー |
US6852176B2 (en) * | 2002-07-17 | 2005-02-08 | Deloro Stellite Holdings Corporation | Wear-resistant, corrosion-resistant cobalt-based alloys |
JP5529366B2 (ja) * | 2007-03-29 | 2014-06-25 | 三菱重工業株式会社 | コーティング材料及びその製造方法並びにコーティング方法並びにシュラウド付き動翼 |
JP6698280B2 (ja) * | 2015-05-15 | 2020-05-27 | 山陽特殊製鋼株式会社 | 合金粉末 |
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2022
- 2022-06-29 WO PCT/JP2022/025968 patent/WO2023277063A1/ja active Application Filing
- 2022-06-29 JP JP2023532017A patent/JPWO2023277063A1/ja active Pending
- 2022-06-29 EP EP22833209.4A patent/EP4343016A1/en active Pending
- 2022-06-29 KR KR1020247002471A patent/KR20240022658A/ko unknown
- 2022-06-29 CN CN202280044120.4A patent/CN117561348A/zh active Pending
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JPWO2023277063A1 (zh) | 2023-01-05 |
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WO2023277063A1 (ja) | 2023-01-05 |
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