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Article(id=1215700944055091467, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1215700941538509036, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202405087, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1715011200000, receivedDateStr=2024-05-07, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1767775291694, onlineDateStr=2026-01-07, pubDate=1721836800000, pubDateStr=2024-07-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1767775291694, onlineIssueDateStr=2026-01-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1767775291694, creator=13701087609, updateTime=1767775291694, updator=13701087609, issue=Issue{id=1215700941538509036, tenantId=1146029695717560320, journalId=1210938733613449225, year='2024', volume='53', issue='7', pageStart='1', pageEnd='158', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1767775291094, creator=13701087609, updateTime=1767775458121, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1215701642159243949, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1215700941538509036, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1215701642159243950, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1215700941538509036, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=143, endPage=148, ext={EN=ArticleExt(id=1215700944327721241, articleId=1215700944055091467, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Mechanism analysis for high-temperature corrosion behaviors of boiler water-wall tube and its arc spraying NiCr coating in a power plant, columnId=1211002405299294959, journalTitle=Thermal Power Generation, columnName=Thermal energy science research, runingTitle=null, highlight=null, articleAbstract=

Under the background of wide application of low nitrogen and oxygen combustion technology and deep peaking technology, the high temperature corrosion failure of water wall tubes is more serious in service process. The high-temperature corrosion behavior characteristics of the boiler water wall tube and high-speed arc spraying PS45 coated tube from a power plant were comparatively investigated. Moreover, the corrosion surface morphology, corrosion products compositions and corrosion cross section characteristics were systematically analyzed by means of SEM, EDS and XRD. The results show that, the high-speed arc spraying PS45 coating can effectively improve the high temperature corrosion resistance of water wall tubes, and the thickness of the surface corrosion layer is small. In the process of high temperature service, the PS45 coating shows better corrosion resistance due to its high content of Cr and Ni, and the thickness of the surface corrosion products layer is thin. However, the microscopic pores between the coating particles will lead to intrusion of high-temperature corrosion reactions, and even cause direct corrosion of the water wall tubes at the coating/substrate interface.

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在低氮氧燃烧技术及深度调峰技术广泛应用的背景下，锅炉水冷壁管在服役过程中的高温腐蚀失效更为严重。对比研究了取自某电厂锅炉水冷壁管及高速电弧喷涂PS45涂层管的高温腐蚀行为特征，利用SEM、EDS、XRD等手段对腐蚀表面形貌特征、腐蚀产物组成及腐蚀截面特征进行了系统分析。结果表明：高速电弧喷涂PS45涂层可有效提高水冷壁管的抗高温腐蚀性能，其表面腐蚀层厚度较小；在高温服役过程中，PS45涂层因其高Cr、Ni元素而表现出更好的抗腐蚀性能，其表面腐蚀产物层较薄，但涂层粒子间的微观孔隙会导致高温腐蚀反应的侵入，甚至导致涂层/基材界面处水冷壁管的直接腐蚀。

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朱秋瑜（2004），女，本科生，主要研究方向为材料科学与工程，。

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朱秋瑜（2004），女，本科生，主要研究方向为材料科学与工程，。

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朱秋瑜（2004），女，本科生，主要研究方向为材料科学与工程，。

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boiler water wall surface, figureFileSmall=h6NulgsonnwIKouxR39phg==, figureFileBig=ahHYxhwPOqX4MxU3Vs9Gjg==, tableContent=null), ArticleFig(id=1215700951973937738, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=CN, label=图7, caption=锅炉水冷壁表面高温腐蚀机理分析示意, figureFileSmall=h6NulgsonnwIKouxR39phg==, figureFileBig=ahHYxhwPOqX4MxU3Vs9Gjg==, tableContent=null), ArticleFig(id=1215700952062018127, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=EN, label=Tab.1, caption=

Composition of the 15CrMoG water wall tube

, figureFileSmall=null, figureFileBig=null, tableContent=
化学元素FeCrMoCSiMn
质量分数/%其余1.030.510.120.200.53
), ArticleFig(id=1215700952145904209, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=CN, label=表1, caption=

水冷壁管材15CrMoG成分

, figureFileSmall=null, figureFileBig=null, tableContent=
化学元素FeCrMoCSiMn
质量分数/%其余1.030.510.120.200.53
), ArticleFig(id=1215700952238178902, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=EN, label=Tab.2, caption=

The PS45 spray coating ingredients

, figureFileSmall=null, figureFileBig=null, tableContent=
化学元素NiCrTi
质量分数/%其余42.000.90
), ArticleFig(id=1215700952351425114, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=CN, label=表2, caption=

PS45喷涂涂层成分

, figureFileSmall=null, figureFileBig=null, tableContent=
化学元素NiCrTi
质量分数/%其余42.000.90
), ArticleFig(id=1215700952439505501, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=EN, label=Tab.3, caption=

Chemical composition analysis of high temperature corrosion cross section of the 15CrMoG tube

, figureFileSmall=null, figureFileBig=null, tableContent=
位置CONaAlSiSKFe
层A2.4725.47000.570.27071.21
层B10.8421.100.644.465.090.410.5356.95
层C2.7723.980001.79071.45
), ArticleFig(id=1215700952527585890, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=CN, label=表3, caption=

15CrMoG管高温腐蚀截面层化学成分分析

, figureFileSmall=null, figureFileBig=null, tableContent=
位置CONaAlSiSKFe
层A2.4725.47000.570.27071.21
层B10.8421.100.644.465.090.410.5356.95
层C2.7723.980001.79071.45
), ArticleFig(id=1215700952640832103, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=EN, label=Tab.4, caption=

Chemical composition analysis of high temperature corrosion crosssection layer of the high speed arc spraying PS45 coating

, figureFileSmall=null, figureFileBig=null, tableContent=
位置COSCrNiTiAl
亮白色6.631.751.2026.4265.20
暗灰色26.116.8056.618.881.140.46
), ArticleFig(id=1215700952728912493, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1215700944055091467, language=CN, label=表4, caption=

高速电弧喷涂PS45涂层高温腐蚀截面层化学成分分析

, figureFileSmall=null, figureFileBig=null, tableContent=
位置COSCrNiTiAl
亮白色6.631.751.2026.4265.20
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某电厂锅炉水冷壁管及表面电弧喷涂NiCr涂层高温腐蚀行为机理分析
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朱秋瑜 1 , 秦建新 2
热力发电 | 热能科学研究 2024,53(7): 143-148
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热力发电 | 热能科学研究 2024, 53(7): 143-148
某电厂锅炉水冷壁管及表面电弧喷涂NiCr涂层高温腐蚀行为机理分析
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朱秋瑜1 , 秦建新2
作者信息
  • 1.西北工业大学伦敦玛丽女王大学工程学院，陕西　西安　710129
  • 2.华能邯峰电厂，河北　邯郸　056200

    • 朱秋瑜（2004），女，本科生，主要研究方向为材料科学与工程，。

Mechanism analysis for high-temperature corrosion behaviors of boiler water-wall tube and its arc spraying NiCr coating in a power plant
Qiuyu ZHU1 , Jianxin QIN2
Affiliations
  • 1.Queen Mary University of London Engineering School, Northwestern Polytechnical University, Xi’an 710129, China
  • 2.Huaneng Hanfeng Power Plant, Handan 056200, China
出版时间: 2024-07-25 doi: 10.19666/j.rlfd.202405087
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摘要
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在低氮氧燃烧技术及深度调峰技术广泛应用的背景下，锅炉水冷壁管在服役过程中的高温腐蚀失效更为严重。对比研究了取自某电厂锅炉水冷壁管及高速电弧喷涂PS45涂层管的高温腐蚀行为特征，利用SEM、EDS、XRD等手段对腐蚀表面形貌特征、腐蚀产物组成及腐蚀截面特征进行了系统分析。结果表明：高速电弧喷涂PS45涂层可有效提高水冷壁管的抗高温腐蚀性能，其表面腐蚀层厚度较小；在高温服役过程中，PS45涂层因其高Cr、Ni元素而表现出更好的抗腐蚀性能，其表面腐蚀产物层较薄，但涂层粒子间的微观孔隙会导致高温腐蚀反应的侵入，甚至导致涂层/基材界面处水冷壁管的直接腐蚀。

水冷壁  /  高温腐蚀  /  腐蚀机理  /  电弧喷涂  /  NiCr涂层

Under the background of wide application of low nitrogen and oxygen combustion technology and deep peaking technology, the high temperature corrosion failure of water wall tubes is more serious in service process. The high-temperature corrosion behavior characteristics of the boiler water wall tube and high-speed arc spraying PS45 coated tube from a power plant were comparatively investigated. Moreover, the corrosion surface morphology, corrosion products compositions and corrosion cross section characteristics were systematically analyzed by means of SEM, EDS and XRD. The results show that, the high-speed arc spraying PS45 coating can effectively improve the high temperature corrosion resistance of water wall tubes, and the thickness of the surface corrosion layer is small. In the process of high temperature service, the PS45 coating shows better corrosion resistance due to its high content of Cr and Ni, and the thickness of the surface corrosion products layer is thin. However, the microscopic pores between the coating particles will lead to intrusion of high-temperature corrosion reactions, and even cause direct corrosion of the water wall tubes at the coating/substrate interface.

water wall  /  high temperature corrosion  /  corrosion mechanism  /  arc spraying  /  NiCr coating
朱秋瑜, 秦建新. 某电厂锅炉水冷壁管及表面电弧喷涂NiCr涂层高温腐蚀行为机理分析. 热力发电, 2024 , 53 (7) : 143 -148 . DOI: 10.19666/j.rlfd.202405087
Qiuyu ZHU, Jianxin QIN. Mechanism analysis for high-temperature corrosion behaviors of boiler water-wall tube and its arc spraying NiCr coating in a power plant[J]. Thermal Power Generation, 2024 , 53 (7) : 143 -148 . DOI: 10.19666/j.rlfd.202405087
正文
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燃煤发电是我国最主要的发电来源，截至2023年末，煤炭发电量超过全国总发电量的50%[1]。在“双碳”背景下，为满足国家能源结构调整以及环保需求，燃煤发电厂普遍存在深度调峰和低氮燃烧问题[2-4]。深度调峰造成水冷壁表面温度变化剧烈，而低氮氧燃烧会产生大量的还原性腐蚀气氛，这会加剧锅炉水冷壁管表面的腐蚀，因此对电厂锅炉水冷壁管表面的抗腐蚀性能提出了更高的要求[5]。
通常燃煤电厂水冷壁管材为铁素体钢，其耐高温腐蚀性较差，难以抵挡高温条件下腐蚀性气氛和壁面结焦产物的腐蚀作用。随着腐蚀的深入，水冷壁管壁厚逐渐减薄，最终出现服役过程中的爆管现象，从而导致发电装备的非正常停机，造成巨大的经济损失[6-7]。为此，在水冷壁表面制备具有优异抗腐蚀性能的防护涂层技术已广泛应用于电站锅炉装备。其中，热喷涂技术因其涂层加工效率高、良好的现场加工适应性及工艺成本相对较低等优势，在当前火电燃煤锅炉受热面防护中应用最为广泛。Oksa等人[8]采用锅高速火焰喷涂技术在锅炉管道表面制备了3种不同的Ni-Cr涂层，经过2年实际现场运行，3种涂层均表现出优异的耐腐蚀性。韩运华[9]通过对高温硫化动力曲线分析，结果表明Cr质量分数大于40%的45CT镍铬合金涂层耐硫腐蚀性能相当于碳钢的60倍，证明喷涂制备的Ni-Cr涂层具有较强抵抗腐蚀的能力。虽然，当前已有诸多关于锅炉管道及防护涂层高温腐蚀的研究，但对深度调峰和低氮燃烧技术条件下锅炉水冷壁及表面电弧喷涂涂层的腐蚀特性研究较少，相关内在腐蚀机理尚不清楚。
为此，本文针对某电厂锅炉水冷壁管及高速电弧喷涂PS45涂层后管材开展腐蚀性能及其机理分析，评价电弧喷涂涂层在水冷壁腐蚀防护中的应用效果及特征。本文的研究结果不仅可为深度调峰和低氮燃烧背景下电厂锅炉水冷壁表面防护提供技术参考，还可丰富锅炉水冷壁表面的腐蚀行为理论，对水冷壁表面防护技术及涂层材料开发奠定基础。
1　实验内容
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1.1　实验材料
本文中分析的样管取自某燃煤电厂600 MW机组锅炉现场水冷壁，该水冷壁管材及其表面电弧喷涂样件实际服役6个月。水冷壁管材料为15CrMoG，其规格为Φ63.5 mm×7.0 mm，化学成分见表1。为了提高水冷壁管表面的抗腐蚀性能，采用高速电弧喷涂技术在其表面制备了PS45涂层，其化学成分见表2。
1.2　腐蚀表面形貌及产物分析
为了分析水冷壁管及涂层的高温腐蚀行为，利用扫描电子显微镜（SEM）Hitachi SU3500对15CrMoG水冷壁管及电弧PS45涂层的腐蚀表面形貌及腐蚀截面形貌特征进行观察分析。采用X射线衍射仪（XRD）Bruker D8ADVANCE对水冷壁表面腐蚀产物进行物相表征，以分析其腐蚀反应过程。利用SEM结合能谱（EDS）Oxford分析，表征水冷壁管表面及界面附近的元素分布特征。
2　实验结果与讨论
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2.1　锅炉水冷壁高温腐蚀表面形貌
图1为现场服役6个月后的15CrMoG水冷壁管及电弧喷涂PS45涂层后的管件照片。从图1a)可以看出，15CrMoG管材表面呈现明显的红褐色，附着较厚的红褐色、黑色与白色混合腐蚀产物，且腐蚀表面较为粗糙。该表面腐蚀形貌说明，在高温服役过程中，水冷壁管表面发生严重的腐蚀。相比之下，表面喷涂PS45涂层后的水冷壁表面较为光滑，整体呈现灰白色，说明带有防护涂层的水冷壁抗腐蚀性能明显提升。此外，在服役后的管表面未发现明显的开裂和剥落现象，由此说明在深度调峰背景下电弧喷涂PS45涂层在服役6个月后仍可保持较好的服役安全性。
利用SEM对服役后的15CrMoG管材和PS45涂层表面进行观察，水冷壁管材腐蚀后表面腐蚀层形貌如图2所示。由图2a)可以看出，15CrMoG管材表面附着明显的高温腐蚀产物层，在腐蚀层表面分布着大量球形颗粒状的腐蚀产物。通过高倍形貌观察（图2b)），腐蚀表面产物呈现疏松状态，说明层内存在诸多孔隙。另一方面，在腐蚀表面可以观察到明显的裂纹，通常腐蚀产物层中孔隙和裂纹的存在不利于材料的抗腐蚀性，主要因为裂纹会成为腐蚀性介质（气体及液态等）向内扩展通道。
相比之下，高速电弧喷涂PS45涂层表面腐蚀产物表面未发现明显的开裂（图2c)），这有利于阻碍腐蚀反应的进一步进行，从而提高其抗高温腐蚀性能。虽然低倍下电弧喷涂PS45涂层高温腐蚀表面形态特征与15CrMoG管表面类似，均表现为球形颗粒状腐蚀表面形貌，但从高倍图像中可发现涂层表面腐蚀产物层相对更加致密，可较好地阻碍高温下腐蚀介质的扩散和侵入性腐蚀，从而提高其抗腐蚀性。然而，高速电弧喷涂PS45涂层高温服役后表面出现剥落特征，这可能由深度调峰过程中水冷壁表面温差变化引起的应力变化导致[10]。
2.2　锅炉水冷壁及涂层高温腐蚀表面物相组成
图3为服役后15CrMoG管材以及高速电弧喷涂PS45涂层腐蚀表面的X射线衍射图谱。从图3可以看出，经历6个月烟气腐蚀后，15CrMoG管材表面腐蚀产物由Fe2O3、Fe3O4、FeS2、FeS、Fe2(SO4)3、Na3Fe(SO4)3、K3Fe(SO4)3、SiO2、Al2O3构成，其中Fe的氧化物（Fe2O3、Fe3O4）质量分数为93.21%，Fe的硫化物（FeS2、FeS）质量分数为1.34%。说明高温服役过程中水冷壁管表面主要发生氧化和硫化腐蚀反应。根据水冷壁管的化学成分可以推断，管表面的腐蚀产物层中不仅含有管材高温腐蚀后的产物，还含有部分煤炭燃烧后的烟气结焦产物。在高温烟气中，煤炭燃烧产生的碱金属氧化物（Na2O、K2O等）和SO2、SO3等硫氧化物进行反应生成碱金属盐，在水冷壁表面沉积并熔化而造成熔盐腐蚀，因此腐蚀产物中含有Na3Fe(SO4)3、K3Fe(SO4)3[11]。另一方面，煤炭中的黄铁矿（FeS2）在高温下与水冷壁管表面发生反应生成FeS[12-13]。总体而言，在高温服役工况下，水冷壁管表面受到高温烟气和结焦产物的腐蚀作用，生成铁的氧化物（Fe2O3、Fe3O4）、硫化物（FeS）以及复合硫酸盐。
图3b)为高速电弧喷涂PS45涂层在腐蚀6个月后的高温腐蚀表面XRD图谱。
从图3中可以看出，PS45涂层高温腐蚀后的表面产物由CrO、Cr2O3、Fe2O3、NiCrO4、NiCr2O4、Cr6S7、FeS2、Na2SO4、K2SO4、SiO2、Al2O3组成。其中Cr的氧化物（CrO、Cr2O3）质量分数为80.32%，Cr酸盐（NiCrO4、NiCr2O4）质量分数为11.16%，Cr的硫化物（Cr6S7）质量分数为6.18%。相比于未喷涂保护的水冷壁管，PS45涂层表面腐蚀产物层中形成了Cr的氧化物以及Ni、Cr复合氧化物[14]。镍铬氧化物具有尖晶石结构，且易形成致密产物层，有利于阻挡高温下腐蚀性烟气和熔盐的向内扩散腐蚀。因此，高速电弧喷涂PS45涂层表现在更加优异的抗高温腐蚀性能。
2.3　锅炉水冷壁及涂层高温腐蚀界面特征
为分析锅炉水冷壁管在现场服役过程中的腐蚀行为及内在机理，本文对高温服役后管材的腐蚀横截面进行了系统的表征观察（图4）。图4a)为15CrMoG管材高温腐蚀截面的背散射SEM图像。从图4可以看出，管材表面的高温腐蚀层的平均厚度约为50 μm，腐蚀层内部存在大量贯通式裂纹，不利于形成保护性腐蚀产物层，该结果与腐蚀表面形貌观察结果一致。
根据腐蚀产物层内部不同部位的形态特征，可将其分为表层连续层（层A）、中间疏松层（层B）和底层破裂层（层C）3层。表3给出了图4a)中腐蚀产物层不同部位的平均化学元素成分。基于化学元素分析结果可知，层A主要由Fe、O和C元素组成，为铁的氧化物层，其平均厚度约为8 μm；层B主要由C、O、Al、Si和Fe等元素组成，主要为结焦产物层，其平均厚度约为22 μm；层C主要由C、O、S和Fe元素组成，主要为硫化物和氧化物混合层。
由于低氮改造造成水冷壁附近为强还原性气氛，在煤炭燃烧过程中产生大量H2S、CO气体[15]。高温烟气与沉积在结焦层的C共同作用造成水冷壁管材出现硫化物腐蚀。同时结焦层中的碱金属硫酸盐（Na2SO4、K2SO4）造成了水冷壁管材出现硫酸盐腐蚀，二者共同作用形成了硫化物富集层。结焦层的产生主要由于烟气的碱金属盐蒸气在较低温度的水冷壁表面易发生凝结，而以胞状晶形态凝结的碱金属造成了管壁表面粘性增大，进一步将高温烟气中部分高熔点的Al2O3、SiO2及未完全燃烧的C吸附，从而形成较厚的结焦层。氧化产物层位于结焦层之外，说明其为煤炭燃烧结束后，在结焦层表面形成的。在煤炭燃烧结束后，水冷壁表面附近的氧分压升高，而造成结焦层中的FeS、FeS2发生高温氧化反应，同时Fe元素向外扩散形成的相应的氧化物层。
图5为高速电弧喷涂PS45涂层服役后的高温腐蚀截面的背散射SEM图像。由图5a)可以看出，PS45涂层的平均厚度约为200 μm，且在涂层内部存在明显的亮白色和暗灰色区域。在服役6个月后，涂层表面可以观察到较薄的腐蚀产物层，且在涂层与基体界面处也可观察到暗灰色组织。涂层表面的腐蚀产物层厚度明显低于15CrMoG管材表面，说明PS45涂层表现出更为优异的抗高温腐蚀性能，该结果与服役后水冷壁管的表面形貌分析结果一致。在高温腐蚀环境下，PS45涂层中的Cr元素会优先发生氧化反应而形成致密的Cr2O3表面产物膜，该产物膜可对高温腐蚀作用发挥较好的阻碍作用。
根据能谱面扫描结果可见，亮色区域明显为富Ni区，而暗灰色区域为富O、Cr和S的区域，说明其可能为腐蚀产物。进一步通过能谱点扫描分析，具体结果见表4。由表4可知：亮色区域主要含有Ni、Cr元素，说明其为未腐蚀的涂层区域；而暗灰色区域主要富含Cr和O元素，说明其为高温腐蚀后的区域。对于电弧喷涂PS45涂层，其在涂层沉积过程中，涂层粒子间以机械结合的形式堆积，因此粒子间通常存在微观间隙而影响涂层的致密性。在高温服役过程中，腐蚀性高温烟气及熔盐会研喷涂粒子间隙向其内部扩散，进而发生腐蚀反应。Goebel等人研究发现[16]，在还原性气氛条件下，铬的氧化物会先于γ-（Ni，Cr）固溶体与烟气中的H2S、SO2气体及活性S发生硫化反应，并释放出O2气体加剧涂层内部的微孔缺陷问题，使得腐蚀性气体可以向涂层更深的内部进行侵入。由于Cr元素会优先向腐蚀界面扩散而发生氧化反应，涂层中未腐蚀区域的Cr元素质量分数相应降低，而腐蚀产物中Cr元素质量分数相对较高。
此外，进一步对涂层基材界面处的暗灰色组织进行元素成分分析，结果如图6所示。从图6可以看出，该区域与涂层内部暗灰色腐蚀区域成分明显不同，其主要为O、S和Fe的富集区，而Cr和Ni的质量分数相对较低。由此可以推断，该暗灰色组织为碳钢基体发生氧化和硫化腐蚀而生成的，并非涂层腐蚀后的产物。该腐蚀产物层的平均厚度约为10 μm，明显低于15CrMoG管材表面的腐蚀层厚度，也证明了高速电弧喷涂PS45涂层的抗腐蚀效果。然而，该现象说明在服役6个月后，带有高速电弧喷涂PS45涂层的水冷壁管已经发生严重的侵入性腐蚀，腐蚀沿喷涂粒子间隙深入涂层与基材界面处，在后续使用中存在涂层大面积剥落的风险。
2.4　锅炉水冷壁高温腐蚀机理
本文通过对某电厂锅炉水冷壁管材进行高温腐蚀表面及腐蚀截面进行系统分析，可以推断在当前深度调峰工程及低氮改造技术背景下水冷壁管及电弧喷涂涂层的高温腐蚀机理。首先，在煤炭燃烧过程中，水冷壁表面主要受到还原性气氛下的硫化物高温腐蚀及硫酸盐高温腐蚀。在还原性气氛条件下，S元素主要以H2S气体形式存在，会水冷壁表面铁基氧化膜反应，进而与基体中的金属M(Fe\Cr)发生腐蚀反应；此外，H2S会与CO及结焦层中的未燃尽C共同作用破坏氧化膜，从而加剧腐蚀反应。黄铁矿（FeS2）受热分解会释放出MS和活性S单质，活性S具有比H2S更强的腐蚀能力，其不仅会破坏表面氧化膜，还会穿透基体表面的腐蚀层沿着基体晶间向内渗透，造成晶间腐蚀[17]。另一方面，煤炭在燃烧过程中生成的碱金属氧化物会与烟气中的SO3、SO2反应生成熔融态碱金属硫酸盐，其在水冷壁表面沉积并与金属氧化膜以及金属基体腐蚀反应，生成焦硫酸盐（Na2S2O7、K2S2O7）和碱金属盐（Na3M(SO4)3、K3M(SO4)3）等复合硫酸盐。这些复合硫酸盐又会进一步与无氧化膜保护的基体反应，生成熔点更低的碱金属硫酸盐，从而加剧水冷壁管材表面的腐蚀。
图7为15CrMoG管材及喷涂PS45涂层后管材的高温腐蚀行为机理示意。在高温烟气和熔盐腐蚀条件下，15CrMoG管材中Fe元素发生严重的硫化和氧化腐蚀反应，在其表面形成较厚的腐蚀产物层，但该腐蚀产物层中裂纹和孔隙较多，难以发挥阻碍腐蚀的作用。
然而，电弧喷涂PS45涂层内部含有较高的Ni、Cr元素，在高温腐蚀过程中Cr2O3氧化膜对高温烟气和熔盐腐蚀发挥一定阻碍作用，有利于其抗腐蚀性能提高。然而，由于喷涂过程中涂层粒子间存在微观孔隙，在高温腐蚀过程中腐蚀性气体与熔盐可沿粒子间隙向涂层内部扩散发生侵入性腐蚀。随着服役时间的增长，高温腐蚀会侵入至涂层基体界面，直接造成水冷壁管基材的腐蚀，从而严重影响涂层的抗腐蚀性能及服役安全可靠性。因此，通过提高涂层的致密性可有效改善其抗高温腐蚀性能及对水冷壁管的保护效果。
3　结论
收起
本文主要针对某电厂水冷壁管材及喷涂防护后的管材进行了高温腐蚀行为研究，发现了15CrMoG管材和高速电弧喷涂PS45涂层不同的抗高温腐蚀行为特征及机理，得出如下主要结论。
1）深度调峰及超低排放的运行工况下，锅炉水冷壁管表面腐蚀机理主要受到还原性气氛下的硫化物高温腐蚀及硫酸盐的混合型高温腐蚀。
2）15CrMoG管材腐蚀表面产物层呈现氧化层、富焦层和富硫层3层，但腐蚀层内部较为疏松且发生严重的开裂现象，难以形成对基体的保护。
3）高速电弧喷涂PS45涂层对锅炉水冷壁管表面具有较好的防护作用，可有效提高水冷壁的抗高温腐蚀性能。
4）高速电弧喷涂PS45涂层中较高的Ni、Cr元素可发挥较好的抗高温腐蚀作用；但涂层粒子间的微观孔隙会导致腐蚀性元素的向内扩散腐蚀，在长期服役后腐蚀会侵入至涂层/基材界面处，导致基材的直接腐蚀。
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doi: 10.19666/j.rlfd.202405087
  • 接收时间：2024-05-07
  • 首发时间：2026-01-07
  • 出版时间：2024-07-25
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  • 收稿日期：2024-05-07
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    1.西北工业大学伦敦玛丽女王大学工程学院，陕西　西安　710129
    2.华能邯峰电厂，河北　邯郸　056200
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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