Article(id=1322276059316335222, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000835, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000835, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1734364800000, receivedDateStr=2024-12-17, revisedDate=null, revisedDateStr=null, acceptedDate=1737475200000, acceptedDateStr=2025-01-22, onlineDate=1793184779241, onlineDateStr=2026-10-28, pubDate=1789833600000, pubDateStr=2026-09-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793184779241, onlineIssueDateStr=2026-10-28, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793184779241, creator=13701087609, updateTime=1793184779241, updator=13701087609, issue=Issue{id=1322276007797702769, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='9', pageStart='1', pageEnd='252', issueExtLink='null', onlineDate='null', pubDate='1789833600000', pubDateStr='2026-09-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=0, createTime=1793184766959, creator='13701087609', updateTime=1793185369041, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322278533200728093, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322278533200728094, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1322276007797702769, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=140, endPage=149, ext={EN=ArticleExt(id=1322276059547021943, articleId=1322276059316335222, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=High-temperature oxidation behavior of 310S stainless steel fabricated by selective laser melting, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

The isothermal oxidation mass gain test is adopted to study the high-temperature oxidation behavior at 800 ℃ of 310S stainless steel prepared by selective laser melting (SLM) and cold rolling (CR). The microstructure, oxidation kinetics, and oxide scale structure of SLM-310S and CR-310S are systematically analyzed. The results show that both SLM-310S and CR-310S exhibit a single-phase austenite structure. SLM-310S forms a fish-scale structure due to molten pool stacking, characterized by fine and uniform grains, each containing numerous columnar and cellular subgrains. In contrast, CR-310S has typical polygonal austenite grains containing numerous twins. During oxidation at 800 ℃, the mass gain of SLM-310S is lower than that of CR-310S, with oxidation rate constants of 5.612×10-4 mg2·cm-4·h-1 (SLM-310S) and 8.593×10-4 mg2·cm-4·h-1 (CR-310S), respectively. Both specimens develop a double-layer oxide scale: the scale on SLM-310S is approximately 2-4 μm thick and mainly composes of SiO₂, Cr₂O₃ and MnCr₂O₄, while that on CR-310S additionally contains a small amount of Fe-containing oxides, along with pore defects within the matrix. Owing to its excellent microstructural characteristics, SLM-310S exhibits slower oxidation kinetics and a denser oxide scale, demonstrating superior high-temperature oxidation resistance at 800 ℃ compared to CR-310S.

, authors=Xiang LIU1, 2, 3, 4, Kui WEN2, 3, 4, Yongjun HU1, Min LIU2, 3, 4, Jinguo CHEN2, 3, 4, Taikai LIU2, 3, 4, Chen SONG2, 3, 4, authorsList=Xiang LIU, Kui WEN, Yongjun HU, Min LIU, Jinguo CHEN, Taikai LIU, Chen SONG, authorCompany=null, correspAuthors=Kui WEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322276062998934157, articleId=1322276059316335222, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=选区激光熔化310S不锈钢的高温氧化行为, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

采用恒温氧化增重实验研究选区激光熔化(selective laser melting,SLM)技术和冷轧(cold rolling,CR)两种工艺制备的310S不锈钢的800 ℃高温氧化行为,系统分析SLM-310S和CR-310S的显微组织、氧化动力学和氧化膜结构。结果表明:SLM-310S和CR-310S均为单相奥氏体组织,其中SLM-310S因熔池堆叠形成鱼鳞状结构,晶粒细小均匀且单个晶粒内部存在大量柱状、胞状亚晶粒,CR-310S则为典型多边形奥氏体晶粒,晶内伴有大量孪晶组织;800 ℃氧化过程中,SLM-310S的氧化增重低于CR-310S。SLM-310S、CR-310S的氧化速率常数分别为5.612×10-4、8.593×10-4 mg2·cm-4·h-1;两种试样氧化膜均呈双层结构,SLM-310S氧化层厚度约为2~4 μm,主要由SiO₂、Cr₂O₃和MnCr₂O₄组成,CR-310S氧化膜中还含有少量含Fe氧化物,且基体内部存在孔洞缺陷。SLM-310S凭借优异的组织特征,展现出更缓慢的氧化动力学过程与更致密的氧化膜,表明其在800 ℃下的高温抗氧化性能优于CR-310S。

, authors=刘香1, 2, 3, 4, 文魁2, 3, 4, 胡永俊1, 刘敏2, 3, 4, 陈金果2, 3, 4, 刘太楷2, 3, 4, 宋琛2, 3, 4, authorsList=刘香, 文魁, 胡永俊, 刘敏, 陈金果, 刘太楷, 宋琛, authorCompany=null, correspAuthors=文魁, authorNote=null, correspAuthorsNote=
文魁(1985—),男,高级工程师,博士,研究方向为表面工程技术、增材制造,联系地址:广东省广州市天河区长兴路363号广东省科学院新材料研究所表面实验楼227室(510650),E-mail:
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Chemical compositions of SLM-310S and CR-310S (mass fraction/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleCSiMnPSCrNiFe
SLM-310S0.0081.371.700.0070.00625.8321.12Bal.
CR-310S0.040.530.860.0220.00125.7619.32Bal.
), ArticleFig(id=1322276071353987816, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276059316335222, language=CN, label=表1, caption=

SLM-310S和CR-310S的化学成分(质量分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleCSiMnPSCrNiFe
SLM-310S0.0081.371.700.0070.00625.8321.12Bal.
CR-310S0.040.530.860.0220.00125.7619.32Bal.
), ArticleFig(id=1322276071404319465, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276059316335222, language=EN, label=Table 2, caption=

EDS analysis results of different regions in Fig.6(atom fraction/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
RegionOSiCrMnFeNi
161.550.1334.202.121.320.67
256.630.2726.7713.371.901.07
34.512.4617.070.8255.3419.80
44.993.3416.730.2555.2119.48
550.830.1647.120.590.840.46
654.160.2535.636.043.290.63
), ArticleFig(id=1322276071475622634, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276059316335222, language=CN, label=表2, caption=

图6中不同区域的EDS分析结果(原子分数/%)

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RegionOSiCrMnFeNi
161.550.1334.202.121.320.67
256.630.2726.7713.371.901.07
34.512.4617.070.8255.3419.80
44.993.3416.730.2555.2119.48
550.830.1647.120.590.840.46
654.160.2535.636.043.290.63
), ArticleFig(id=1322276071542731499, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276059316335222, language=EN, label=Table 3, caption=

EDS analysis results of different regions in Fig.7(atom fraction/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
RegionOSiCrMnFeNi
750.790.0535.640.3812.920.22
838.750.2248.571.7110.460.30
939.9838.3915.634.831.17
1033.640.3053.172.4810.010.40
), ArticleFig(id=1322276071643394796, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1322276059316335222, language=CN, label=表3, caption=

图7中不同区域的EDS分析结果(原子分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
RegionOSiCrMnFeNi
750.790.0535.640.3812.920.22
838.750.2248.571.7110.460.30
939.9838.3915.634.831.17
1033.640.3053.172.4810.010.40
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选区激光熔化310S不锈钢的高温氧化行为
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刘香 1, 2, 3, 4 , 文魁 2, 3, 4 , 胡永俊 1 , 刘敏 2, 3, 4 , 陈金果 2, 3, 4 , 刘太楷 2, 3, 4 , 宋琛 2, 3, 4
材料工程 | 研究论文 2026,54(9): 140-149
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材料工程 |研究论文 2026 , 54 (9) : 140 -149
选区激光熔化310S不锈钢的高温氧化行为
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刘香1, 2, 3, 4, 文魁2, 3, 4 , 胡永俊1, 刘敏2, 3, 4, 陈金果2, 3, 4, 刘太楷2, 3, 4, 宋琛2, 3, 4
作者信息
  • 1.广东工业大学 材料与能源学院,广州 510006
  • 2.广东省科学院 新材料研究所 现代材料表面工程技术国家工程实验室,广州 510650
  • 3.广东省科学院 新材料研究所 特种材料表面工程全国重点实验室,广州 510650
  • 4.广东省科学院 新材料研究所 广东省现代表面工程技术重点实验室,广州 510650
通讯作者:
文魁(1985—),男,高级工程师,博士,研究方向为表面工程技术、增材制造,联系地址:广东省广州市天河区长兴路363号广东省科学院新材料研究所表面实验楼227室(510650),E-mail:
High-temperature oxidation behavior of 310S stainless steel fabricated by selective laser melting
Xiang LIU1, 2, 3, 4, Kui WEN2, 3, 4 , Yongjun HU1, Min LIU2, 3, 4, Jinguo CHEN2, 3, 4, Taikai LIU2, 3, 4, Chen SONG2, 3, 4
Affiliations
  • 1.School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006,China
  • 2.National Engineering Laboratory of Modern Materials Surface Engineering Technology,Institute of New Materials,Guangdong Academy of Sciences,Guangzhou 510650,China
  • 3.State Key Laboratory of Special Materials Surface Engineering,Institute of New Materials,Guangdong Academy of Sciences,Guangzhou 510650,China
  • 4.Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology,Institute of New Materials,Guangdong Academy of Sciences,Guangzhou 510650,China
出版时间: 2026-09-20 doi: 10.11868/j.issn.1001-4381.2024.000835
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采用恒温氧化增重实验研究选区激光熔化(selective laser melting,SLM)技术和冷轧(cold rolling,CR)两种工艺制备的310S不锈钢的800 ℃高温氧化行为,系统分析SLM-310S和CR-310S的显微组织、氧化动力学和氧化膜结构。结果表明:SLM-310S和CR-310S均为单相奥氏体组织,其中SLM-310S因熔池堆叠形成鱼鳞状结构,晶粒细小均匀且单个晶粒内部存在大量柱状、胞状亚晶粒,CR-310S则为典型多边形奥氏体晶粒,晶内伴有大量孪晶组织;800 ℃氧化过程中,SLM-310S的氧化增重低于CR-310S。SLM-310S、CR-310S的氧化速率常数分别为5.612×10-4、8.593×10-4 mg2·cm-4·h-1;两种试样氧化膜均呈双层结构,SLM-310S氧化层厚度约为2~4 μm,主要由SiO₂、Cr₂O₃和MnCr₂O₄组成,CR-310S氧化膜中还含有少量含Fe氧化物,且基体内部存在孔洞缺陷。SLM-310S凭借优异的组织特征,展现出更缓慢的氧化动力学过程与更致密的氧化膜,表明其在800 ℃下的高温抗氧化性能优于CR-310S。

选区激光熔化  /  310S不锈钢  /  抗氧化性能  /  高温氧化

The isothermal oxidation mass gain test is adopted to study the high-temperature oxidation behavior at 800 ℃ of 310S stainless steel prepared by selective laser melting (SLM) and cold rolling (CR). The microstructure, oxidation kinetics, and oxide scale structure of SLM-310S and CR-310S are systematically analyzed. The results show that both SLM-310S and CR-310S exhibit a single-phase austenite structure. SLM-310S forms a fish-scale structure due to molten pool stacking, characterized by fine and uniform grains, each containing numerous columnar and cellular subgrains. In contrast, CR-310S has typical polygonal austenite grains containing numerous twins. During oxidation at 800 ℃, the mass gain of SLM-310S is lower than that of CR-310S, with oxidation rate constants of 5.612×10-4 mg2·cm-4·h-1 (SLM-310S) and 8.593×10-4 mg2·cm-4·h-1 (CR-310S), respectively. Both specimens develop a double-layer oxide scale: the scale on SLM-310S is approximately 2-4 μm thick and mainly composes of SiO₂, Cr₂O₃ and MnCr₂O₄, while that on CR-310S additionally contains a small amount of Fe-containing oxides, along with pore defects within the matrix. Owing to its excellent microstructural characteristics, SLM-310S exhibits slower oxidation kinetics and a denser oxide scale, demonstrating superior high-temperature oxidation resistance at 800 ℃ compared to CR-310S.

selective laser melting  /  310S stainless steel  /  antioxidant property  /  high temperature oxidation
刘香, 文魁, 胡永俊, 刘敏, 陈金果, 刘太楷, 宋琛. 选区激光熔化310S不锈钢的高温氧化行为. 材料工程, 2026 , 54 (9) : 140 -149 . DOI: 10.11868/j.issn.1001-4381.2024.000835
Xiang LIU, Kui WEN, Yongjun HU, Min LIU, Jinguo CHEN, Taikai LIU, Chen SONG. High-temperature oxidation behavior of 310S stainless steel fabricated by selective laser melting[J]. Journal of Materials Engineering, 2026 , 54 (9) : 140 -149 . DOI: 10.11868/j.issn.1001-4381.2024.000835
固体氧化物燃料电池(solid oxide fuel cell,SOFC)因其全固态结构、转换效率高、环境友好等特点,在大型电厂和交通运输领域展现出广阔的应用前景[1]。SOFC系统中的热平衡辅助部件(hot balance of plant,Hot-BOP)在苛刻的服役环境下易遭受热和水蒸气等气氛的腐蚀[2-4],其内部流道结构难以用涂层进行保护,因此,Hot-BOP部件的材料必须具备良好的高温力学性能和抗氧化性能[1]。国内SOFC正处于产业发展前期,产业链断层且BOP部件层面缺失,关于Hot-BOP部件用材料方面的研究报道较少。在高温锅炉、超超临界发电水冷堆包壳等领域的高温部件同样面临苛刻的高温气氛腐蚀服役环境,这些部件材料主要包括Ni基高温合金和Fe基耐热不锈钢。Ni基合金性能优越,是一种耐腐蚀性好、强度高、疲劳寿命长、可在650 ℃以上进行长期工作的高温合金[5],但其价格昂贵,是普通耐热钢的5倍甚至更高。耐热不锈钢是含有一定量Ni和Cr的Fe基合金,高温下Cr含量的增加会促进表面氧化膜的形成,而较高的Ni含量可以提高氧化物的稳定性[6-7]。因此,某些Fe基合金能以良好的力学性能和卓越的耐腐蚀性、耐高温性代替昂贵的镍基合金[8-9]。310S被认为是高温下耐腐蚀性能较好的不锈钢之一[10],其在高温太阳能热系统碳酸盐熔体中的耐腐蚀性能要远高于304和316L两种不锈钢[11],而在高温、高压超临界CO2环境下的抗氧化性能也要优于800H合金,证实了310S在高温、高压超临界CO2环境下的抗氧化性能比800H合金更优越[12]。将310S长期暴露在700 ℃的蒸气和超临界水环境中,其表面生成的致密Cr2O3层对基体起到很好的保护作用[13]。
当前国内开发的SOFC系统所用Hot-BOP部件主要为自主设计或海外定制,通常体积较大,降低了发电系统的功率密度。开发具有高紧凑复杂结构的Hot-BOP是未来SOFC行业的一个重要发展方向。而采用传统加工方式难以实现这类复杂结构BOP的精细化成形要求。选区激光熔化(selective laser melting,SLM)是一种基于三维数值模型实现产品成形的增材制造技术,能够实现对结构的精细和均匀控制[14-15],非常适用于复杂结构件[16]。而且其还具有加工速度快、节能环保、节省成本等优点[17-19],为高紧凑、低流阻的Hot-BOP部件成形提供了一条全新可行的技术路线。采用SLM制备的合金在某些性能方面要优于传统加工,例如,经SLM制备的316L不锈钢在800 ℃具有优异的抗拉强度和相对较高的伸长率[20],SLM制备的GH4099合金在500、700、900 ℃的力学性能均优于冷轧板[21],但是关于SLM技术制备310S不锈钢在高温氧化性能方面的研究报道较少。
本工作通过对比分析SLM态和冷轧态310S不锈钢在显微组织、结构等方面的差异,评估二者在Hot-BOP服役温度下的抗氧化性能,为SLM技术成形310S不锈钢等材质的Hot-BOP部件在发电系统中的应用提供实验数据支撑。
本工作使用选区激光熔化成形态和冷轧态两种310S不锈钢试样,分别记为SLM-310S和CR-310S,二者的化学成分如表1所示。SLM-310S不锈钢粉末由湖南特种金属材料有限责任公司提供,粉末形貌及粒径分布如图1所示。可见,粉末球形度较高,主要为球形或近球形,部分粉末表面出现“卫星”粉末黏附现象,粉末粒径为12~40 μm,其中D10、D50和D90分别为18.2、25.3 μm和34.5 μm。成形工艺参数为:扫描速度700 mm/s,激光功率160 W,扫描层厚度40 μm,扫描间隔0.1 mm,成形试样尺寸30 mm×10 mm×2.5 mm。CR-310S不锈钢板由山西太钢不锈钢股份有限公司提供,经电火花线切割加工为30 mm×10 mm×2.5 mm尺寸试样。
使用SiC砂纸(400#~2000#)、金刚石抛光膏、腐蚀剂(50 mL HCl+5 g FeCl3)制备金相试样。根据GB/T 13303—1991标准,采用静态氧化不连续法对两种试样进行800 ℃恒温氧化增重实验。将试样打磨、抛光至镜面,随后置于无水乙醇中超声清洗,烘干后采用游标卡尺测量试样尺寸并计算表面积。将试样放入高于实验温度100 ℃灼烧至恒重的刚玉坩埚中,使用精度为0.1 mg的电子天平称量试样和坩埚总质量。氧化实验在KSL 1200X型箱式电阻炉中进行,氧化至指定时间后依次取出称重。
SLM-310S原材料粉末粒径采用激光粒度仪(Mastersizer 3000)进行测量;利用光学显微镜(Leica-DMI5000 M)观察试样的金相组织;使用X射线衍射仪(Bruker D8 Advance)对分别氧化0、100、300、500 h后的SLM-310S、CR-310S、SLM-310S原材料粉末进行物相分析,扫描速度为2 (°)/min,扫描范围为10°~90°;利用扫描电子显微镜(Nova-nano-450)观察氧化后试样的氧化膜表面及截面微观形貌,并用配备的能谱仪(EDS)分析氧化膜元素成分及分布情况。
图2为试样XRD谱图及局部放大图。由图2(a)可知,所有试样和原材料粉末均为单相奥氏体结构,表明选区激光熔化过程未改变材料的相组成。图2(b)为图2(a)在2θ=48°~77°范围内的局部放大图,可以观察到,SLM-310S试样的(220)面衍射峰半峰宽(full width at half maximum, FWHM)与SLM-310S原材料粉末相比更宽,表明SLM-310S试样(220)面的晶面间距减小,晶粒尺寸得到细化,同时(200)面衍射峰的强度降低,说明在打印过程中晶粒在该晶面上发生择优取向[22]。
图3为SLM-310S和CR-310S的显微组织。可以看出,不同成形工艺下的两种试样在金相组织结构上表现出明显差异。打印试样的显微组织通常分为横向扫描层组织与纵向叠加层组织,本工作SLM-310S的所有测试表征面均为平行于成形方向的纵向叠加层,如图3(a)所示。SLM-310S的结构因熔池堆叠呈现为典型的鱼鳞状,相邻熔池搭接紧密,熔池边界清晰可见,单个晶粒内部存在大量胞状及柱状亚晶粒,且柱状晶表现为一定的外延性。这种结构特征源于成形过程中的非平衡凝固方式及激光束快速移动造成的温度梯度,晶粒倾向于沿最大热度梯度方向生长,当热量从熔池边界向内部传递时,柱状晶得以充分生长并穿过熔池边界,部分受多个熔池边界交叉影响的区域则容易生成等轴胞状晶。从图3(b)中可以看到,CR-310S晶粒呈现为典型的多边形奥氏体晶粒,并存在大量孪晶组织。与CR-310S相比,SLM-310S的晶粒更细小均匀。
图4为SLM-310S和CR-310S在800 ℃氧化500 h后的单位面积氧化增重(W)曲线及氧化增重动力学曲线。可以看出,试样的质量均随氧化时间的增加呈现出增长的趋势。在氧化0~100 h内,二者的质量均出现大幅增加;在氧化100~300 h时,质量增加幅度放缓;而在氧化300~500 h时,增重趋于平稳。这是由于氧化开始时试样表面完全暴露在空气中,在800 ℃下迅速发生氧化反应,随着氧化时间的增加,试样表面开始生成保护性氧化膜,抑制氧元素向基体扩散及基体内部元素向外扩散,从而控制氧化程度。氧化至一定程度后,氧化膜结构趋于稳定,试样质量变化逐渐平缓。然而,在500 h整个氧化过程中,CR-310S的氧化增重始终高于SLM-310S试样的。产生这种现象的主要原因在于,SLM-310S拥有更细小的晶粒尺寸,较大的晶界体积分数为元素扩散迁移提供了更多通道,因此在SLM-310S试样表面更容易生成保护性氧化膜[23]。此外,两种试样的氧化规律均呈抛物线型,根据瓦格纳氧化理论,氧化动力学行为可由式(1)描述。
W2=Kp⋅t+C
式中:Kp为氧化速率常数;t为氧化时间,s; C为常数。根据式(1)对试样的氧化时间与单位面积氧化增重平方的关系进行拟合,如图4(b)所示,可以看出整体拟合程度较好。同时通过式(1)计算获得SLM-310S和CR-310S两种试样在800 ℃的氧化速率常数分别为5.612×10-4 mg2·cm-4·h-1和8.593×10-4 mg2·cm-4·h-1。SLM-310S试样所对应的氧化速率常数更小,表现出较慢的氧化动力学过程,这进一步说明SLM-310S试样在800 ℃下具有优于CR-310S试样的抗高温氧化性能。
图5为SLM-310S和CR-310S在800 ℃分别氧化100、300 h和500 h的XRD谱图。从图5(a)可以看出,SLM-310S的氧化膜主要由Cr2O3和MnCr2O4组成,γ相为基体相,且γ相的衍射峰始终为SLM-310S的主峰,这可能与SLM-310S的氧化膜较薄甚至出现脱落有关。随着氧化时间的延长,XRD谱图中物相组成保持稳定,仅衍射峰强度发生变化,表明SLM-310S氧化膜的成分稳定,但氧化物的含量发生变化。由图5(b)可知,CR-310S的氧化膜主要由Cr2O3、MnCr2O4/Fe3O4组成。氧化100 h时,仅观测到Cr2O3相与γ相的衍射峰。随着氧化时间的增加,逐渐出现MnCr2O4/Fe3O4衍射峰,且该衍射峰强度随氧化时间增加逐渐增强,主峰Cr2O3相的衍射峰强度则表现出与之相反的趋势,表明在氧化100 h时MnCr2O4与Fe3O4占比极少甚至没有,后续随着氧化的进行,其含量逐渐增加,但在氧化500 h内,CR-310S氧化膜仍然由Cr2O3主导。
为了深入探究氧化膜形貌及其结构变化,图6给出SLM-310S在800 ℃氧化不同时间的表面形貌。可以看出,氧化100 h后,SLM-310S表面氧化膜出现轻微剥落,但整体平整性较好。产生这种现象的原因,可能是SLM-310S成形热应力在高温氧化过程中逐渐释放的结果。由氧化100 h的放大图可以看到,试样表面生成由尖晶石和片状结构氧化物组成的均匀致密氧化膜,表层尖晶石颗粒尺寸在1~2 μm之间,底层间隙则被尺寸更小的尖晶石颗粒填充,片状氧化物随机夹杂在尖晶石颗粒中。氧化300 h后,试样表面的氧化膜出现较大面积脱落,脱落区域存在明显凹坑,放大图中呈现的未发生脱落区域几乎完全被尖晶石覆盖,片状结构氧化物明显减少。与氧化100 h相比,300 h氧化后氧化物之间结合更紧密,氧化膜致密度提高,但平整性略差。氧化500 h后,氧化膜脱落区域的边缘重新生成一层薄膜状的氧化物,且在高倍SEM中并未见到片状氧化物,氧化试样表面生成大量团聚状的细小氧化物颗粒,这种结构的氧化物与规则的八面体状尖晶石颗粒共同作用,提高了氧化膜的致密度,但在一定程度上影响表面的平整度。
图6中1~6区的EDS分析结果,如表2所示。1区和2区的元素成分结合图5(a)的XRD谱图分析表明,尖晶石为MnCr2O4,片状氧化物为Cr2O3。在出现脱落的3区和4区,均检测到较高的Si元素含量,表明脱落氧化物与基体之间还生成了少量的SiO2。对氧化500 h后的5区进行元素分析发现,新生成的氧化膜结构主要为富Cr氧化物,而团聚生长的氧化物颗粒为Cr2O3与MnCr2O4(6区)。
图7为CR-310S氧化不同时间的表面形貌。与SLM-310S相比,CR-310S的氧化膜结构有所不同,主要以片状结构的氧化物为主,且表面起伏,氧化物之间的间隙较大。氧化100 h时,CR-310S表面氧化膜几乎由片状氧化物组成,氧化物之间存在一定厚度差,偏厚的氧化物倾向于聚集生长,增加了氧化膜表面的起伏。当氧化时间达到300 h后,氧化膜表面无明显变化,仍以片状氧化物为主,但片状氧化物平均厚度减小,团聚情况减少,氧化膜相较100 h明显平整。此外,表面还发现少量尖晶石氧化物,其颗粒尺寸大约为5 μm,远远大于SLM-310S尖晶石颗粒尺寸。图7(c)为氧化500 h后的表面形貌,较长的氧化时间使得尖晶石含量进一步增加,片状氧化物则保持较高的稳定性,大面积粘附在基体上。整个氧化过程中试样表面未发现明显的剥落或开裂区域,氧化膜展现出较高的完整性,但坩埚内存在少量脱落的氧化皮,说明CR-310S的表面也出现了氧化皮脱落的现象。
为探究CR-310S的氧化膜组成,对图7中7~10区域进行EDS成分分析,结果见表3。可以看到, CR-310S氧化膜中片状氧化物成分是Cr2O3,尖晶石颗粒的主要成分是MnCr2O4。除此之外,7~10区域均检测到Fe元素,说明Fe元素已经扩散至氧化膜表面。
图8为SLM-310S和CR-310S氧化不同时间的截面SEM图。可以看出,二者表面均形成连续的氧化膜结构。由图8(a-1),(b-1),(c-1)可知,氧化过程中基体结构始终保持良好,内部没有明显缺陷,氧化层厚度为2~4 μm。产生这种现象的原因是,SLM成形态的试样晶粒细小,提高了择优氧化元素的扩散通量,使得氧化初期Mn元素快速扩散,并在表面与Cr2O3结合生成Mn-Cr尖晶石,从而阻止氧元素向内扩散及Cr元素向外扩散,大幅降低试样的氧化速度。另外,氧化100 h后SLM-310S的氧化膜结构相对疏松,300、500 h氧化后,氧化膜致密度明显提升;氧化膜的厚度在前300 h基本保持稳定,氧化至500 h时,厚度略微增加。这是由于氧化后期Cr2O3与尖晶石团聚生长,增加了表面的起伏与氧化膜厚度。CR-310S的截面形貌如图8(a-2),(b-2),(c-2)所示,氧化层与基体结合良好,厚度高达9~12 μm,且在不同氧化时间基本保持稳定,但氧化层中间存在些许微孔及横向发展的裂纹,且表层部分的氧化物间隙较大,保护作用不足。此外,在距离基体表面约10 μm范围内出现若干孔洞缺陷,这是由氧化过程中试样内部的Cr和Mn元素向外扩散迁移所留下的。综上所述,虽然SLM-310S的氧化膜与基体之间产生一定程度的开裂,但基体的完好程度仍然优于CR-310S,抗高温氧化性能表现得更加优越。
为了解氧化膜的元素分布,对SLM-310S和CR-310S的氧化膜截面进行EDS分析,分别如图9,10所示。可知,两种试样氧化膜均呈现出双层结构,底层都为富Si氧化层。Si元素具有最高亲氧性,高温氧化时,在基体与富Cr氧化层之间和氧元素快速反应形成底层SiO2氧化层,此类富Si氧化物同样能对基体起到一定的保护作用,有效抑制基体内部元素的扩散。SLM-310S因其略高于CR-310S的Si含量,在一定程度上提高了富Si层的保护作用,但对二者抗氧化性能差异的作用有限。SLM-310S试样主要因其更细小均匀的晶粒,使得底层SiO2更连续,表层由Cr2O3与MnCr2O4组成的氧化膜结构也始终保持更好的致密性,从而表现出更好的抗氧化性能。CR-310S底层Si元素的富集区域比较分散,主要集中在空腔等缺陷区域,表层Cr2O3层中除Mn元素外还存在少量Fe元素,Fe的受氧化程度同样反映了抗氧化性能的优劣[24],进一步说明SLM-310S抗氧化性能更优。
(1)SLM-310S和CR-310S均为单相奥氏体组织,制备工艺决定了二者显微组织的显著差异。SLM-310S受熔池堆叠影响呈鱼鳞状结构,晶粒细小均匀且内部富含柱状、胞状亚晶粒,为氧化元素扩散提供了更高通量;CR-310S则为典型的多边形奥氏体晶粒,晶内存在大量孪晶组织,其元素扩散效率相对更低。
(2)800 ℃恒温氧化条件下,SLM-310S的氧化增重始终低于CR-310S的,其氧化速率常数为5.612×10-4 mg2·cm-4·h-1,远低于CR-310S的8.593×10-4 mg2·cm-4·h-1,说明SLM-310S的氧化动力学过程更缓慢,高温氧化的稳定性更强。
(3)SLM-310S和CR-310S的氧化膜均呈现双层结构,但物相组成、形貌及基体状态差异明显。SLM-310S的氧化层厚度仅2~4 μm,主要由SiO₂、Cr₂O₃和MnCr₂O₄组成,膜层致密无明显缺陷;CR-310S氧化膜除上述主要物相外,还含有少量含Fe氧化物,且因元素过度扩散导致基体内部出现孔洞缺陷,氧化膜防护性更差。
  • 国家重点研发计划项目(2022YFB4003603)
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2026年第54卷第9期
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doi: 10.11868/j.issn.1001-4381.2024.000835
  • 接收时间:2024-12-17
  • 首发时间:2026-10-28
  • 出版时间:2026-09-20
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  • 收稿日期:2024-12-17
  • 录用日期:2025-01-22
基金
国家重点研发计划项目(2022YFB4003603)
作者信息
    1.广东工业大学 材料与能源学院,广州 510006
    2.广东省科学院 新材料研究所 现代材料表面工程技术国家工程实验室,广州 510650
    3.广东省科学院 新材料研究所 特种材料表面工程全国重点实验室,广州 510650
    4.广东省科学院 新材料研究所 广东省现代表面工程技术重点实验室,广州 510650

通讯作者:

文魁(1985—),男,高级工程师,博士,研究方向为表面工程技术、增材制造,联系地址:广东省广州市天河区长兴路363号广东省科学院新材料研究所表面实验楼227室(510650),E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
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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