Article(id=1187029893083709448, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187029888956510427, articleNumber=1009-5438(2024)05-0016-08, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1717171200000, receivedDateStr=2024-06-01, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1760939580460, onlineDateStr=2025-10-20, pubDate=1729785600000, pubDateStr=2024-10-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1760939580460, onlineIssueDateStr=2025-10-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1760939580460, creator=13701087609, updateTime=1760939580460, updator=13701087609, issue=Issue{id=1187029888956510427, tenantId=1146029695717560320, journalId=1185652524569653253, year='2024', volume='50', issue='5', pageStart='1', pageEnd='98', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1760939579476, creator=13701087609, updateTime=1760941227119, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1187036799714083448, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187029888956510427, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1187036799714083449, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1187029888956510427, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=16, endPage=23, ext={EN=ArticleExt(id=1187104195778855591, articleId=1187029893083709448, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Effects and Characterization of Rare Earth Elements on Inclusions in Steel, columnId=null, journalTitle=Science & Technology of Baotou Steel, columnName=null, runingTitle=null, highlight=null, articleAbstract=

The development of high performance rare earth steel with special effects of rare earth elements is of great significances for the utilization of rare earth resources and technological progress of iron and steel in Baotou, while it is the key for developing rare earth steel to clear the quantitative behavior of rare earth in steel. In the paper, the behaviors and mechanisms of rare earth elements in steel are discussed from such aspects as their thermodynamics, nucleation of rare earth inclusions and mechanism of internal friction for rare earth. Moreover, the non destructive characterization methods of rare earth inclusions are introduced.

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利用稀土元素的特殊作用开发高性能稀土钢,对包头稀土资源利用和钢铁技术进步有重要意义,而明晰稀土在钢中的定量行为,是开发稀土钢的关键。文章分别从钢中稀土元素热力学、稀土夹杂物形核、稀土内耗机制等方面探讨了钢中稀土元素的行为和机理,同时介绍了稀土夹杂物的无损伤表征方法。

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王国承(1977-),男,江西省九江市人,博士,教授,现从事高品质钢冶金新理论、新技术研究工作。

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王国承(1977-),男,江西省九江市人,博士,教授,现从事高品质钢冶金新理论、新技术研究工作。

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王国承(1977-),男,江西省九江市人,博士,教授,现从事高品质钢冶金新理论、新技术研究工作。

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反应方程 ΔGθ/(J·mol-1) 反应方程 ΔGθ/(J·mol-1)
2[La]+3[O]=La2O3 -1 443 880+337T[21] 2[Ce]+3[O]=Ce2O3 -1 428 760+359.39T[23]
[La]+[S]=LaS -637 900+227T[22] [Ce]+[S]=CeS -422 100+120.38T[24]
2[La]+3[S]=La2S3 -1 266 000+417.9T[22] 2[Ce]+3[S]=Ce2S3 -1 340 000+497.7T[22]
2[La]+2[O]+[S]=La2O2S -1 341 200+301T[21] 2[Ce]+2[O]+[S]=Ce2O2S -1 351 400+331T[23]
2[Y]+3[O]=Y2O3 -1 792 600+658T[22] 2[Y]+3[S]=Y2S3 -1 171 000+441T[22]
[Y]+[S]=YS -433 800+151.2T[22] 2[Y]+2[O]+[S]=Y2O2S -1 521 000+536T[22]
), ArticleFig(id=1187104391954841741, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1187029893083709448, language=CN, label=表1, caption=

稀土元素与O和S的反应方程及其标准吉布斯自由能变化值

, figureFileSmall=null, figureFileBig=null, tableContent=
反应方程 ΔGθ/(J·mol-1) 反应方程 ΔGθ/(J·mol-1)
2[La]+3[O]=La2O3 -1 443 880+337T[21] 2[Ce]+3[O]=Ce2O3 -1 428 760+359.39T[23]
[La]+[S]=LaS -637 900+227T[22] [Ce]+[S]=CeS -422 100+120.38T[24]
2[La]+3[S]=La2S3 -1 266 000+417.9T[22] 2[Ce]+3[S]=Ce2S3 -1 340 000+497.7T[22]
2[La]+2[O]+[S]=La2O2S -1 341 200+301T[21] 2[Ce]+2[O]+[S]=Ce2O2S -1 351 400+331T[23]
2[Y]+3[O]=Y2O3 -1 792 600+658T[22] 2[Y]+3[S]=Y2S3 -1 171 000+441T[22]
[Y]+[S]=YS -433 800+151.2T[22] 2[Y]+2[O]+[S]=Y2O2S -1 521 000+536T[22]
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稀土元素对钢中夹杂物的影响及其表征
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王国承 1 , 肖远悠 1 , 张达先 2 , 唐建平 2 , 何建中 2
包钢科技 | 2024,50(5): 16-23
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包钢科技 | 2024, 50(5): 16-23
稀土元素对钢中夹杂物的影响及其表征
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王国承1, 肖远悠1, 张达先2, 唐建平2, 何建中2
作者信息
  • 1.辽宁科技大学 材料与冶金学院,辽宁 鞍山 114051
  • 2.内蒙古包钢钢联股份有限公司技术中心,内蒙古 包头 014010
  • 王国承(1977-),男,江西省九江市人,博士,教授,现从事高品质钢冶金新理论、新技术研究工作。

Effects and Characterization of Rare Earth Elements on Inclusions in Steel
Wang Guo-cheng1, Xiao Yuan-you1, Zhang Da-xian2, Tang Jian-ping2, He Jian-zhong2
Affiliations
  • 1. School of Materials and Metallurgy, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
  • 2. Technical Center of Inner Mongolia Baotou Steel Union Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2024-10-25
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利用稀土元素的特殊作用开发高性能稀土钢,对包头稀土资源利用和钢铁技术进步有重要意义,而明晰稀土在钢中的定量行为,是开发稀土钢的关键。文章分别从钢中稀土元素热力学、稀土夹杂物形核、稀土内耗机制等方面探讨了钢中稀土元素的行为和机理,同时介绍了稀土夹杂物的无损伤表征方法。

稀土  /  夹杂物  /  形核  /  内耗  /  表征

The development of high performance rare earth steel with special effects of rare earth elements is of great significances for the utilization of rare earth resources and technological progress of iron and steel in Baotou, while it is the key for developing rare earth steel to clear the quantitative behavior of rare earth in steel. In the paper, the behaviors and mechanisms of rare earth elements in steel are discussed from such aspects as their thermodynamics, nucleation of rare earth inclusions and mechanism of internal friction for rare earth. Moreover, the non destructive characterization methods of rare earth inclusions are introduced.

rare earth  /  inclusions  /  nucleation  /  internal friction  /  characterization
王国承, 肖远悠, 张达先, 唐建平, 何建中. 稀土元素对钢中夹杂物的影响及其表征. 包钢科技, 2024 , 50 (5) : 16 -23 .
Wang Guo-cheng, Xiao Yuan-you, Zhang Da-xian, Tang Jian-ping, He Jian-zhong. Effects and Characterization of Rare Earth Elements on Inclusions in Steel[J]. Science & Technology of Baotou Steel, 2024 , 50 (5) : 16 -23 .
20世纪90年代以来,稀土(RE)在炉外精炼领域获得了广泛应用,极大地推动了稀土处理钢产业的发展,稀土处理钢的作用机制、对钢性能的影响机理也逐渐成熟。目前已确认了稀土具有净化钢液、变质-变性-变形夹杂物以及微合金化等方面的作用,可以显著提高钢产品的韧塑性、高温强度、抗高温氧化性、耐腐蚀性等多方面的综合性能。
总体概括,稀土对钢有下面四个方面的作用:①稀土对钢液有深度净化作用。由于稀土元素很活泼,能够形成稳定的氧化物、硫化物等,在洁净钢中微量稀土可深度脱氧、脱硫、脱磷,减少硫和磷在晶界的偏聚,改善晶界;稀土亦可与砷、锑、铋、铅、锡等低熔点有害元素作用,形成较高熔点的化合物,抑制这些低熔点元素在晶界的偏析。钢液中稀土首先是脱氧,其次脱硫,当钢液里的氧、硫去除到足够干净后,稀土才能去其他杂质,形成的夹杂物上浮到炉渣,达到净化钢液的作用[1-5]。②稀土对夹杂物的具有形态控制和变质作用。稀土能改变钢液中氧化物、硫化物及碳化物的类型、形态、大小和分布,稀土能够使钢液中尺寸较大的尖锐夹杂物转变成尺寸较小的形貌呈现椭球形或者球形的稀土夹杂物[6-10]。③稀土能够改善钢的凝固组织,细化晶粒。稀土与钢液中的合金元素反应能够生成一些细小弥散的夹杂物颗粒,这些夹杂物颗粒散布在钢液中形成许多的形核点,钢液在冷却的过程中以此为形核点,进行非均匀形核,促进晶粒尺寸下降,改善凝固组织[11-15]。④稀土能在钢中微量固溶,实现微合金化。固溶的稀土元素由于与铁原子差别较大,可以作为一种缺陷存在起到强化作用。稀土元素主要通过改变奥氏体晶粒大小及奥氏体与铁素体中沉淀相的析出行为来达到微合金化,使钢的耐磨、耐腐蚀、抗疲劳等性能得到改善[16-20]
稀土元素与钢中硫元素反应的通式如下:
$[\mathrm{RE}]+[\mathrm{S}]=\mathrm{RES}$
$2[\mathrm{RE}]+3[\mathrm{~S}]=\mathrm{RE}_{2} \mathrm{~S}_{3}$
纯物质RES或者RE2S3的活度是1,因此反应(1)和(2)的平衡常数方程式表示如下:
$\lg K_{\mathrm{RES}}=-\lg \left(a_{\mathrm{RE}} a_{\mathrm{S}}\right)=-\lg [\% \mathrm{RE}]-\lg [\% \mathrm{~S}]- \\\lg f_{\mathrm{RE}}-\lg f_{\mathrm{S}}$
$\begin{aligned}\lg K_{\mathrm{RE}_{2} \mathrm{~S}_{3}} & =-\lg \left(a_{\mathrm{RE}}^{2} a_{\mathrm{S}}^{3}\right)=-2 \lg [\% \mathrm{RE}] \\3 \lg [\% \mathrm{~S}]-2 \lg f_{\mathrm{RE}}-3 \lg f_{\mathrm{S}} &\end{aligned}$
稀土元素与钢中氧元素反应的通式如下:
$2[\mathrm{RE}]+3[\mathrm{O}]=\mathrm{RE}_{2} \mathrm{O}_{3}$
纯物质RE2O3的活度是1,反应(5)的平衡常数方程式表示如下:
$\begin{aligned}\lg K_{\mathrm{RE}_{2} \mathrm{O}_{3}} & =-\lg \left(a_{\mathrm{RE}}^{2} a_{\mathrm{O}}^{3}\right)=-2 \lg [\% \mathrm{RE}] \\3 \lg [\% \mathrm{O}]-2 \lg f_{\mathrm{RE}}-3 \lg f_{\mathrm{o}} &\end{aligned}$
另外,稀土元素与钢中氧、硫同时反应生成复合型夹杂物,其反应通式及平衡常数方程如下:
$2[\mathrm{RE}]+2[\mathrm{O}]+[\mathrm{S}]=\mathrm{RE}_{2} \mathrm{O}_{2} \mathrm{~S}$
$\begin{array}{c}\lg K_{\mathrm{RE}_{2} \mathrm{O}_{2} \mathrm{~S}}=-\lg \left(a_{\mathrm{RE}}^{2} a_{0}^{2} a_{\mathrm{S}}\right)=-2 \lg [\% \mathrm{RE}]- \\2 \lg [\% \mathrm{O}]-\lg [\% \mathrm{~S}]-2 \lg f_{\mathrm{RE}}-2 \lg f_{0}-\lg f_{\mathrm{S}}\end{array}$
上述方程(3)、(4)、(6)和(8)中,αifi是钢中稀土元素和S或O的活度及活度系数。其中fi可以由下面方程求得:
$\lg f_{i}=e_{i}^{j} w[j]$
表1给出了稀土元素与O和S的反应方程及其标准吉布斯自由能变化值。
通过计算,分别得到稀土La、Ce、Y与O和S的反应平衡图。稀土元素与钢中氧反应的产物为RE2O3,而与钢中硫反应的产物为两种,分别为RE2S3和RE2O2S。如图1(a)所示,在同样稀土含量情况下,与La、Ce、Y平衡的O,从低到高的顺序是La、Ce、Y。因此,从热力学角度可知,稀土La、Ce、Y的脱氧能力从大到小排列为La、Ce、Y。同理,由图1(b)分析可知,稀土La、Ce、Y的脱硫能力从大到小排列为La、Ce、Y。热力学分析发现,在稀土La与S反应的过程中,当lg[%La]>1.61、lg[%Ce]>0.41和lg[%Y]>1.22时,稀土与S反应的产物由RES转变成RE2S3
图2为La、Ce、Y与O和S的反应优势区图。当钢中O和S含量不同时,同一稀土元素在钢中生成的产物是不同的,这与钢中O/S比有关。O/S比较小时,稀土在钢中与O或S反应的产物为RES或RE2S3。随着O/S比的增加,La和Ce的硫化物会首先转化为RE2O2S,接着转化为RE2O3。然而,对于稀土Y而言,而随着O/S比的增加,Y2S3的变化路径为:Y2S3→Y2O2S→Y2O3,而YS的变化路径可能有两种,为YS→Y2O2S→Y2O3或YS→Y2O3
目前对于钢中夹杂物形核的研究应用最广泛的理论是经典形核理论(Classical Nucleation Theory,CNT)[25-27]。CNT论源于对蒸气中液滴凝聚的研究,现已经将CNT扩展应用到从溶液或者熔体中结晶出固体晶体的研究。对于钢中夹杂物形核问题,CNT有两个作用:第一,用来估计夹杂物形成过程中临界晶核的尺寸;第二,计算夹杂物形核的吉布斯自由能变化[28]。CNT是对单组分蒸气中液滴凝聚形核过程研究而提出来的,而对于多组分的混合物体系其存在明显不足[29]。在稀土夹杂物的形成过程中,涉及到的过程非常复杂,稀土夹杂物的形核是一个多相反应过程,既涉及到化学反应又存在不同物相的转变,其过程十分复杂。CNT只关注夹杂物形核过程中的始末态,而没有给出夹杂物形核长大过程中的中间相(包括团簇、纳米晶体等)结构和性质,因此CNT难以描述稀土夹杂物的形核过程。
为了进一步研究夹杂物形核的问题,冶金工作者尝试用非经典形核理论来阐述其形核过程。近些年,通过原位透射电镜分析技术可以直接观察矿物[30]、固体钢中第二相[7]等二步形核行为。另外,虽然钢液温度高导致还没有实验技术可直接观察夹杂物形核,但一些实验现象已反映出形核过程信息[31-35]。作者前期对夹杂物形核做了大量工作,发现夹杂物形核过程可描述为溶质原子反应→团簇→临界核的两个步骤,并利用二步形核理论(Two-step Nucleation Theory)解释了钢中夹杂物形核的过程问题[34-37]
根据二步形核理论,稀土夹杂物的形核过程包括两步。在钢熔体中,稀土[RE]与[O]或[S]反应首先会生成稀土夹杂物团簇,如图3所示。其反应方程表示如下:
$2[\mathrm{RE}]+3[\mathrm{O}]=1 / n\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n}$
${[\mathrm{RE}]+[\mathrm{S}]=1 / n(\mathrm{RES})_{n}}$
$2[\mathrm{RE}]+3[\mathrm{~S}]=1 / n\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n}$
$2[\mathrm{RE}]+2[\mathrm{O}]+[\mathrm{S}]=1 / n\left(\mathrm{RE}_{2} \mathrm{O}_{2} \mathrm{~S}\right)_{n}$
第二步,稀土夹杂物团簇发生相变,转变成稀土夹杂物晶体,其方程式如下:
$1 / n\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n}=\mathrm{RE}_{2} \mathrm{O}_{3}(\text { 晶体 })$
$1 / n(\mathrm{RES})_{n}=\mathrm{RES}(\text { 晶体 }) $
$1 / n\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n}=\mathrm{RE}_{2} \mathrm{~S}_{3}(\text { 晶体 })$
$1 / n\left(\mathrm{RE}_{2} \mathrm{O}_{2} \mathrm{~S}\right)_{n}=\mathrm{RE}_{2} \mathrm{O}_{2} \mathrm{~S}(\text { 晶体 })$
根据上述反应方程,稀土夹杂物二步形核过程中,团簇的形成及团簇转变成晶体吉布斯自由能变化值计算如下:
$\begin{array}{c}\Delta G_{\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n-1}}=\Delta G_{\mathrm{RE}_{2} \mathrm{O}_{3}(\mathrm{~S})}^{\theta}-\left[\mathrm{G}_{\mathrm{RE}_{2} \mathrm{O}_{3}(\text { 晶体 })}-\right. \\\left.(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n}}\right] \Delta G_{\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n-2}}=G_{\mathrm{RE}_{2} \mathrm{O}_{3}(\text { 晶体 })}-(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{O}_{3}\right)_{n}}\end{array}$
$\begin{array}{c}\Delta G_{(\mathrm{RES})_{n-1}}=\Delta G_{\mathrm{RES}(\mathrm{~S})}^{\theta}-\left[G_{\mathrm{RES}(\text { 晶体 })}-\right. \\\left.(1 / n) G_{(\mathrm{RES})_{n}}\right] \Delta G_{(\mathrm{RES})_{n-2}}=G_{\mathrm{RES}(\text { 晶体 })}-(1 / n) G_{(\mathrm{RES})_{n}}\end{array}$
$\begin{array}{c}\Delta G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n-1}}=\Delta G_{\mathrm{RE}_{2} \mathrm{~S}_{3}(\mathrm{~S})}^{\theta}-\left[\mathrm{G}_{\mathrm{RE}_{2} \mathrm{~S}_{3}(\text { 晶体 })}-\right. \\\left.(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n}}\right] \Delta G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n-2}}=G_{\mathrm{RE}_{2} \mathrm{~S}_{3}(\text { 晶体 })}-(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{3}\right)_{n}}\end{array}$
$\Delta G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}\right)_{n-1}}=\Delta G_{\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}(\mathrm{~S})}^{\theta}-\left[\mathrm{G}_{\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}(\text { 晶体 })}-\right.\left.(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}\right)_{n}}\right] \Delta G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}\right)_{n-2}}=G_{\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}(\text { 晶体 })}-(1 / n) G_{\left(\mathrm{RE}_{2} \mathrm{~S}_{2} \mathrm{O}\right)_{n}}$
式中: G R E 2 O 3 ( )GRES(晶体) G R E 2 S 3 ( ) G R E 2 O 2 S ( )是稀土夹杂物晶体的吉布斯自由能, G R E 2 S O 3 ) n G ( R E S ) n G R E 2 S S 3 ) n G R E 2 O 2 S ) n是稀土夹杂物团簇的吉布斯自由能。稀土夹杂物的晶体和团簇的吉布斯自由能可以通过第一性原理方法计算得到[34-37]
内耗曲线能够反映出稀土元素在钢中的合金化微观机制。作者采用自由衰减法测量变温(室温到400 ℃)下重轨钢、稀土处理后重轨钢的温度-内耗曲线,如图4所示。在未添加稀土的重轨钢内耗曲线上发现三个内耗峰,分别在70 ℃、113 ℃、152 ℃处出现,70 ℃处的内耗峰是Snoek峰,113 ℃处的内耗峰为B峰,152 ℃处的内耗峰为SKK峰。三个峰的激活能分别为0.901 eV、1.019 eV、1.378 eV。在添加稀土的重轨钢内耗曲线上发现三个内耗峰,分别在114 ℃、175 ℃、232 ℃处出现,三个峰的激活能分别为1.019 eV、1.187 eV、1.346 eV。添加稀土后的重轨钢所出现的内耗峰与未添加稀土的重轨钢内耗峰相对应,分别是Snoek峰、B峰和SKK峰,但添加稀土后所有峰的峰温向高温移动。出现Snoek峰的原因是钢中存在着间隙固溶原子,由于在应力的作用下使得间隙原子微扩散所引起的弛豫。B峰是钢中存在固溶的间隙原子与位错交互作用时,交互能为负的情况下,溶质在基体中不会形成均匀分布,它们要偏聚到位错周围,形成所谓“柯氏气团”。此时,位错如果要运动就必须从气团中挣脱出来或者拖着气团一起运动,于是产生了较强的固溶强化效应。SKK峰是重轨钢中位错与间隙溶质原子交互作用引起的弛豫。稀土的加入使得重轨钢的Snoek峰、B峰、SKK峰峰温升高,峰宽更宽,从而使得三个内耗峰的激活能升高,稀土固溶在钢中导致间隙原子微扩散及与位错的交互更困难,提高了重轨钢的韧性。
对于钢中稀土夹杂物的形貌及成分分析,最常用的方法是金相法观察。首先通过对样品钢进行切割、打磨、抛光等步骤制成待观察金相样品,接着采用场发射电子扫描显微镜对钢中夹杂物的形貌及分布情况进行观察,结合能量色散光谱仪对钢中稀土夹杂物的形貌、组成、分布情况进行测定。金相观察的方法只能观察到稀土夹杂物的二维形貌,对于稀土在钢中的整体形貌无法获得。另外,金相分析对于稀土夹杂物在钢中的含量很难做到定量的分析,无法确定钢中固溶稀土和夹杂物中稀土的具体含量。
为了将固溶稀土和夹杂物中稀土无损分离,国内外学者做了大量研究。作者掌握了有机溶液无损提取钢中夹杂物的方法(如图5所示),为钢中稀土夹杂物的无损分离提供了技术保障[38-40]。该方法的主要特点:采用几种有机试剂的混合液作为电解液,保持在低温条件下进行钢样的电解,电解过程中电解液的pH值始终保持在7~8,所以,电解过程中电解液不会产生酸性或碱性物质,从而对钢中的不稳定夹杂物(如MnS、稀土夹杂物等)、极细小(纳米级)夹杂物/析出相等不会产生任何破坏作用,收集到的夹杂物/第二相完整地保留了它们在钢中的原始形貌,方便用于准确的定量分析和扫描电镜、XRD等观察分析。因此,该方法为准确研究钢中夹杂物/析出物的大小、数量、形貌及结构等奠定了很好的基础。
图6为利用有机溶液电解从稀土处理的钢中分离的夹杂物三维形貌。将分离出来的夹杂物、以及电解产生的溶液分别进行化学检测分析,从而分别得到固溶稀土和夹杂物中稀土含量。钢中固溶稀土的总含量计算如下:
$\mathrm{RE} \%=\frac{I_{\mathrm{sp}} \cdot V_{\mathrm{sp}} \cdot W \cdot 100}{I_{\mathrm{RE}} \cdot V_{\mathrm{RE}} \cdot \Delta g}$
钢的夹杂物中稀土的含量:
$\mathrm{RE} \%=\frac{I_{\mathrm{inc}} \cdot V_{\mathrm{inc}} \cdot W \cdot 100}{I_{\mathrm{RE}} \cdot V_{\mathrm{RE}} \cdot \Delta g}$
式中:Isp是溶解试样酸溶液中RE的计数率,imp/(mL·min);Vsp是溶解试样的酸溶液总量,mL;Iinc是溶解夹杂物的酸溶液中RE的计数率,imp/(mL·min);Vinc是溶解夹杂物的酸溶液总量,mLg是溶解在酸溶液中的试样重量,g;IRE是纯RE溶解在酸溶液中的计数率,imp/(mL·min);VRE是溶解纯RE酸溶液的总量,mL;W是溶解在酸溶液中的纯RE的重量,g。图7为钢中固溶稀土含量与钢中总稀土含量的关系。
(1)稀土La、Ce、Y的脱氧或者脱硫能力从大到小排列为La、Ce、Y。稀土脱氧或脱硫产物与钢中O/S比有关,随着O/S比增加其产物变化为:RE2S3/RES→RE2O2S→RE2O3,其中Y还可以从YS直接转成Y2O3
(2)稀土夹杂物的形核过程包括两步:[RE]与[O]或[S]反应→稀土夹杂物团簇→稀土夹杂物晶体。
(3)添加稀土后,重轨钢的Snoek峰、B峰、SKK峰峰温升高,峰宽更宽,稀土固溶在钢中导致间隙原子微扩散及与位错的交互更困难,从而使得三个内耗峰的激活能升高。
  • 白云鄂博稀土资源研究与综合利用国家重点实验室开放课题(2022-141)
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  • 接收时间:2024-06-01
  • 首发时间:2025-10-20
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  • 收稿日期:2024-06-01
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白云鄂博稀土资源研究与综合利用国家重点实验室开放课题(2022-141)
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    1.辽宁科技大学 材料与冶金学院,辽宁 鞍山 114051
    2.内蒙古包钢钢联股份有限公司技术中心,内蒙古 包头 014010
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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