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Article(id=1241416391752994857, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.03.031, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1735056000000, receivedDateStr=2024-12-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773906332195, onlineDateStr=2026-03-19, pubDate=1748707200000, pubDateStr=2025-06-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773906332195, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773906332195, creator=13701087609, updateTime=1773906332195, updator=13701087609, issue=Issue{id=1241416382559081210, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='3', pageStart='1', pageEnd='223', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773906330003, creator=13701087609, updateTime=1773908015401, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241423451685179940, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241423451685179941, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241416382559081210, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=185, endPage=190, ext={EN=ArticleExt(id=1241416392054984774, articleId=1241416391752994857, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Precipitation Behavior of Ti-Containing Inclusions During Solidification of Ti Microalloyed High-Strength Steel, columnId=1236276108207902848, journalTitle=Mining and Metallurgical Engineering, columnName=MATERIALS, runingTitle=null, highlight=null, articleAbstract=

Effects of elements Ti and N on the precipitation behavior of TiN inclusions during the solidification of Timicroalloyed high-strength steel were studied by thermodynamic calculation and microscopic analysis. Thermodynamic calculation results indicate that the precipitation of TiN inclusions is unavoidable at the solidification front, but can be delayed by reducing the value of w(N)0×w(Ti)0. The final size of TiN inclusions is mainly affected by the initial nitrogen content in molten steel, and TiN inclusions can be smaller by reducing the initial nitrogen content. Microscopic analysis shows that with the contents (mass fraction) of Ti and N decreasing from 0.12% and 0.005% to 0.08% and 0.003%, respectively, the number density and average size of TiN inclusions can be decreased by 27.1% and 50.2%, which also confirms the thermodynamic calculation results.

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通过热力学计算结合显微分析的方法，研究了钛微合金化高强钢中Ti、N元素对钢液凝固过程中TiN夹杂物析出行为的影响。热力学计算结果表明：TiN夹杂物在钢液凝固前沿的析出行为是无法避免的，但可以通过减小w（N）0×w（Ti）0的值来延缓TiN夹杂物析出；TiN夹杂物最终尺寸主要受钢液中初始N含量的影响，减小初始N含量可以缩小TiN夹杂物的尺寸。显微分析结果显示，Ti和N元素含量（质量分数）由0.12%和0.005%分别减小到0.08%和0.003%时，TiN夹杂物的数密度和平均尺寸分别下降了27.1%和50.2%，进一步证实了热力学的计算结果。

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孔令男（1986—），男，吉林长春人，博士，副教授，主要研究方向为高强钢、耐磨钢等先进钢铁材料的组织与性能调控。Email：
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刘爱华（1987—），女，吉林长春人，硕士研究生，主要研究方向为高强钢的组织与力学性能。Email：

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刘爱华（1987—），女，吉林长春人，硕士研究生，主要研究方向为高强钢的组织与力学性能。Email：

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刘爱华（1987—），女，吉林长春人，硕士研究生，主要研究方向为高强钢的组织与力学性能。Email：

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Iron and Steel, 2022, 57(3): 44-54., articleTitle=Effect of solute partition coefficient and TiN precipitation on micro-segregation of 22MnB5 steel, refAbstract=null)], funds=[Fund(id=1241422275317125480, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, awardId=2023JJ50481, language=CN, fundingSource=湖南省自然科学基金(2023JJ50481), fundOrder=null, country=null), Fund(id=1241422275455537516, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, awardId=ZSC2023Y37; ZSC2023Y46, language=CN, fundingSource=湖南人文科技学院研究生科研创新项目(ZSC2023Y37; ZSC2023Y46), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241422258565075651, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, xref=1., ext=[AuthorCompanyExt(id=1241422258573464261, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, companyId=1241422258565075651, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.School of Energy and Electromechanical Engineering, Hunan University of Humanities, Science and Technology, Loudi 417000, Hunan, China), AuthorCompanyExt(id=1241422258581852871, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, companyId=1241422258565075651, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.湖南人文科技学院　能源与机电工程学院，湖南　娄底　417000)]), AuthorCompany(id=1241422260070830804, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, xref=2., ext=[AuthorCompanyExt(id=1241422260079219415, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, companyId=1241422260070830804, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.Hunan Valin Lianyuan Iron and Steel Co., Ltd., Loudi 417009, Hunan, China), AuthorCompanyExt(id=1241422260091802329, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, companyId=1241422260070830804, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.湖南华菱涟源钢铁有限公司，湖南　娄底　417009)])], figs=[ArticleFig(id=1241422269310881920, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Fig.1, caption=Segregation ratios of elements Ti and N in steel at different cooling rates, figureFileSmall=+FxZireqJ/9nnu487w+VZg==, figureFileBig=PsIvzIDrmhzvDuN7M2JUhw==, tableContent=null), ArticleFig(id=1241422269445099661, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=图1, caption=钢中Ti和N元素在不同冷却速率下的偏析比

（a）Ti；（b）N

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（a）N；（b）Ti

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（a）N；（b）Ti

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（a）N；（b）Ti

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（a）N；（b）Ti

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（a）纯TiN夹杂物；（b），（c）TiN+氧化物/硫化物复合型夹杂物；（d）氧化物/硫化物夹杂物

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（a）纯TiN夹杂物；（b），（c）TiN+氧化物/硫化物复合型夹杂物；（d）氧化物/硫化物夹杂物

, figureFileSmall=tmmZ1+bpY5xdFywpsM7hnA==, figureFileBig=tO7Fe2zRJ5ljG9/n0fP3tw==, tableContent=null), ArticleFig(id=1241422271609360651, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 1, caption=

Chemical composition of steel used in calculation

, figureFileSmall=null, figureFileBig=null, tableContent=
CSiMnAlTiNb
0.0710.131.850.030.100.05
CrMoNPSFe
0.230.210.0060.010.000 5余量
), ArticleFig(id=1241422271831658768, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表1, caption=

计算所用钢化学成分（质量分数）

, figureFileSmall=null, figureFileBig=null, tableContent=
CSiMnAlTiNb
0.0710.131.850.030.100.05
CrMoNPSFe
0.230.210.0060.010.000 5余量
), ArticleFig(id=1241422271961682198, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 2, caption=

△tl(i) and △ts(i) values

, figureFileSmall=null, figureFileBig=null, tableContent=
元素△tl（i）△ts（i）
C65175
Mn530
Si820
Ti2040
N90—
P30280
S25575
), ArticleFig(id=1241422273551323425, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表2, caption=

△tl（i）和△ts（i）值

, figureFileSmall=null, figureFileBig=null, tableContent=
元素△tl（i）△ts（i）
C65175
Mn530
Si820
Ti2040
N90—
P30280
S25575
), ArticleFig(id=1241422273664569638, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 3, caption=

Equilibrium distribution coefficient and diffusion coefficient of each element

, figureFileSmall=null, figureFileBig=null, tableContent=
元素kD/（cm2·s-1）
C0.340.076 1exp[-143 511/（RT）]
Si0.520.30exp[-251 458/（RT）]
Mn0.780.055exp[-249 366/（RT）]
P0.130.010exp[-182 841/（RT）]
S0.0352.4exp[-223 425/（RT）]
N0.480.91exp[-168 600/（RT）]
Ti0.300.15exp[-250 000/（RT）]
), ArticleFig(id=1241422273769427240, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表3, caption=

各元素的平衡分配系数和扩散系数

, figureFileSmall=null, figureFileBig=null, tableContent=
元素kD/（cm2·s-1）
C0.340.076 1exp[-143 511/（RT）]
Si0.520.30exp[-251 458/（RT）]
Mn0.780.055exp[-249 366/（RT）]
P0.130.010exp[-182 841/（RT）]
S0.0352.4exp[-223 425/（RT）]
N0.480.91exp[-168 600/（RT）]
Ti0.300.15exp[-250 000/（RT）]
), ArticleFig(id=1241422273891062065, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 4, caption=

Interaction coefficients of Ti and N with each element

, figureFileSmall=null, figureFileBig=null, tableContent=
元素与各元素的相互作用系数
CSiMnPSNTiCrAl
N0.130.047-0.020.0450.0070-0.53-0.047-0.028
Ti-0.192.1-0.43-0.006 4-0.11-2.030.0130.055—
), ArticleFig(id=1241422273995919671, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表4, caption=

Ti和N与各元素的相互作用系数

, figureFileSmall=null, figureFileBig=null, tableContent=
元素与各元素的相互作用系数
CSiMnPSNTiCrAl
N0.130.047-0.020.0450.0070-0.53-0.047-0.028
Ti-0.192.1-0.43-0.006 4-0.11-2.030.0130.055—
), ArticleFig(id=1241422274084000061, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 5, caption=

Parameters for calculating growth of TiN inclusions

, figureFileSmall=null, figureFileBig=null, tableContent=
MTiN/（kg·mol-1）ρTiN/（kg·m-3）MFe/（kg·mol-1）ρm/（kg·m-3）
0.0625 3940.0567 070
), ArticleFig(id=1241422274188857668, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表5, caption=

计算TiN夹杂物长大所需部分参数

, figureFileSmall=null, figureFileBig=null, tableContent=
MTiN/（kg·mol-1）ρTiN/（kg·m-3）MFe/（kg·mol-1）ρm/（kg·m-3）
0.0625 3940.0567 070
), ArticleFig(id=1241422274348241225, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 6, caption=

Solid fraction corresponding to TiN inclusions at different initial N and Ti contents

, figureFileSmall=null, figureFileBig=null, tableContent=
元素初始含量/%不同初始w（N）0×w（Ti）0积下的TiN夹杂物凝固分数
2×10-84×10-86×10-88×10-810×10-8
N0.0020.958 80.907 70.853 70.811 20.768 9
0.0040.958 40.907 90.853 40.811 60.768 2
0.0050.958 50.907 80.853 60.811 90.768 9
0.0060.958 80.908 20.853 40.811 80.768 6
0.0080.958 60.908 20.853 20.811 50.768 6
Ti0.050.958 90.908 30.853 30.811 40.768 8
0.100.958 80.908 40.853 50.811 90.769 1
0.120.958 90.908 30.853 50.811 50.768 6
0.150.958 70.908 10.853 40.812 10.768 7
0.200.958 80.907 90.853 60.811 70.768 6
), ArticleFig(id=1241422274478264652, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表6, caption=

不同初始N含量和Ti含量时TiN夹杂物的凝固分数

, figureFileSmall=null, figureFileBig=null, tableContent=
元素初始含量/%不同初始w（N）0×w（Ti）0积下的TiN夹杂物凝固分数
2×10-84×10-86×10-88×10-810×10-8
N0.0020.958 80.907 70.853 70.811 20.768 9
0.0040.958 40.907 90.853 40.811 60.768 2
0.0050.958 50.907 80.853 60.811 90.768 9
0.0060.958 80.908 20.853 40.811 80.768 6
0.0080.958 60.908 20.853 20.811 50.768 6
Ti0.050.958 90.908 30.853 30.811 40.768 8
0.100.958 80.908 40.853 50.811 90.769 1
0.120.958 90.908 30.853 50.811 50.768 6
0.150.958 70.908 10.853 40.812 10.768 7
0.200.958 80.907 90.853 60.811 70.768 6
), ArticleFig(id=1241422274738311503, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 7, caption=

Chemical composition of experimental steels

, figureFileSmall=null, figureFileBig=null, tableContent=
编号CSiMnAlTiNb
1#0.0710.121.830.030.120.05
2#0.0710.141.840.030.080.05
编号CrMoNPSFe
1#0.260.190.0050.010.0005余量
2#0.240.190.0030.010.0005余量
), ArticleFig(id=1241422274851557718, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表7, caption=

实验用钢化学成分（质量分数）

, figureFileSmall=null, figureFileBig=null, tableContent=
编号CSiMnAlTiNb
1#0.0710.121.830.030.120.05
2#0.0710.141.840.030.080.05
编号CrMoNPSFe
1#0.260.190.0050.010.0005余量
2#0.240.190.0030.010.0005余量
), ArticleFig(id=1241422274948026713, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=EN, label=Table 8, caption=

Inclusions in 1# and 2# as-cast

, figureFileSmall=null, figureFileBig=null, tableContent=
铸坯编号夹杂物类型扫描面积/mm2夹杂总数数密度/（个·mm-2）平均尺寸/μm
1#总夹杂物35.5785023.905.46
TiN35.573489.786.14
复合型35.5747713.414.97
氧/硫化物35.57250.706.40
2#总夹杂物44.4673116.443.51
TiN44.463177.133.06
复合型44.463367.563.60
氧/硫化物44.46781.754.53
), ArticleFig(id=1241422275061272928, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241416391752994857, language=CN, label=表8, caption=

1#、2#铸坯中夹杂物统计表

, figureFileSmall=null, figureFileBig=null, tableContent=
铸坯编号夹杂物类型扫描面积/mm2夹杂总数数密度/（个·mm-2）平均尺寸/μm
1#总夹杂物35.5785023.905.46
TiN35.573489.786.14
复合型35.5747713.414.97
氧/硫化物35.57250.706.40
2#总夹杂物44.4673116.443.51
TiN44.463177.133.06
复合型44.463367.563.60
氧/硫化物44.46781.754.53
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钛微合金化高强钢凝固过程中钛夹杂物的析出行为研究
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刘爱华 1 , 孔令男 1 , 李春辉 2 , 齐江华 2 , 陈志国 1 , 阳宇晨 1 , 李菲 1
矿冶工程杂志 | 材料 2025,45(3): 185-190
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矿冶工程杂志 | 材料 2025, 45(3): 185-190
钛微合金化高强钢凝固过程中钛夹杂物的析出行为研究
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刘爱华1 , 孔令男1 , 李春辉2, 齐江华2, 陈志国1, 阳宇晨1, 李菲1
作者信息
  • 1.湖南人文科技学院　能源与机电工程学院，湖南　娄底　417000
  • 2.湖南华菱涟源钢铁有限公司，湖南　娄底　417009

    • 刘爱华（1987—），女，吉林长春人，硕士研究生，主要研究方向为高强钢的组织与力学性能。Email：

通讯作者:

孔令男（1986—），男，吉林长春人，博士，副教授，主要研究方向为高强钢、耐磨钢等先进钢铁材料的组织与性能调控。Email：
Precipitation Behavior of Ti-Containing Inclusions During Solidification of Ti Microalloyed High-Strength Steel
Aihua LIU1 , Lingnan KONG1 , Chunhui LI2, Jianghua QI2, Zhiguo CHEN1, Yuchen YANG1, Fei LI1
Affiliations
  • 1.School of Energy and Electromechanical Engineering, Hunan University of Humanities, Science and Technology, Loudi 417000, Hunan, China
  • 2.Hunan Valin Lianyuan Iron and Steel Co., Ltd., Loudi 417009, Hunan, China
出版时间: 2025-06-01 doi: 10.3969/j.issn.0253-6099.2025.03.031
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摘要
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通过热力学计算结合显微分析的方法，研究了钛微合金化高强钢中Ti、N元素对钢液凝固过程中TiN夹杂物析出行为的影响。热力学计算结果表明：TiN夹杂物在钢液凝固前沿的析出行为是无法避免的，但可以通过减小w（N）0×w（Ti）0的值来延缓TiN夹杂物析出；TiN夹杂物最终尺寸主要受钢液中初始N含量的影响，减小初始N含量可以缩小TiN夹杂物的尺寸。显微分析结果显示，Ti和N元素含量（质量分数）由0.12%和0.005%分别减小到0.08%和0.003%时，TiN夹杂物的数密度和平均尺寸分别下降了27.1%和50.2%，进一步证实了热力学的计算结果。

微合金化  /  高强钢  /  热力学  /  夹杂物  /  TiN  /  析出行为  /  钛  /  氮

Effects of elements Ti and N on the precipitation behavior of TiN inclusions during the solidification of Timicroalloyed high-strength steel were studied by thermodynamic calculation and microscopic analysis. Thermodynamic calculation results indicate that the precipitation of TiN inclusions is unavoidable at the solidification front, but can be delayed by reducing the value of w(N)0×w(Ti)0. The final size of TiN inclusions is mainly affected by the initial nitrogen content in molten steel, and TiN inclusions can be smaller by reducing the initial nitrogen content. Microscopic analysis shows that with the contents (mass fraction) of Ti and N decreasing from 0.12% and 0.005% to 0.08% and 0.003%, respectively, the number density and average size of TiN inclusions can be decreased by 27.1% and 50.2%, which also confirms the thermodynamic calculation results.

microalloying  /  high-strength steel  /  thermodynamics  /  inclusion  /  TiN  /  precipitation behavior  /  titanium  /  nitrogen
刘爱华, 孔令男, 李春辉, 齐江华, 陈志国, 阳宇晨, 李菲. 钛微合金化高强钢凝固过程中钛夹杂物的析出行为研究. 矿冶工程杂志, 2025 , 45 (3) : 185 -190 . DOI: 10.3969/j.issn.0253-6099.2025.03.031
Aihua LIU, Lingnan KONG, Chunhui LI, Jianghua QI, Zhiguo CHEN, Yuchen YANG, Fei LI. Precipitation Behavior of Ti-Containing Inclusions During Solidification of Ti Microalloyed High-Strength Steel[J]. Mining and Metallurgical Engineering, 2025 , 45 (3) : 185 -190 . DOI: 10.3969/j.issn.0253-6099.2025.03.031
正文
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低成本高强钢的使用对船舶、高层建筑、桥梁、汽车、工程装备等轻量化有着重要意义。为了获取低成本高强钢，在通过控轧控冷技术生产的同时辅以向钢中添加一种或多种微合金元素，可以获取更小的晶粒尺寸和更优异的综合力学性能[1-2]。目前使用较多的微合金元素为Nb、V和Ti，单独或组合添加都可以在钢中形成相对稳定的氮化物、碳化物或碳氮化物，这些析出物会起到细晶强化、位错强化和第二相强化等作用[3-6]。其中，Ti元素易与C、N原子组合形成TiN和TiC，TiN产生的沉淀强化效果很好，通过钉扎作用缩小奥氏体尺寸[7]。然而，Ti元素性质活泼，在高温下易与钢中的O、N、C结合生成较大的带有棱角的夹杂物，影响钢基体的连续性，对钢材的抗疲劳性能、延性、韧性、焊接性能及耐腐蚀性能都有不利影响[5,8-10]。因此，为了确保钢的性能和质量，需要控制钢中的钛夹杂物数量和尺寸。本文从大尺寸TiN夹杂物产生的源头入手，借助热力学计算并结合显微分析，对凝固过程中的元素偏析、夹杂物析出和长大过程进行分析，明确TiN夹杂物析出的影响因素，可为提高高强钢性能提供理论参考。
1　实验材料及方法
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实验原料为LG700T钛微合金化高强钢。首先，通过理论计算，明确TiN夹杂物析出的热力学条件及其最终尺寸的影响因素。然后，在某钢企采用200 t顶底复吹转炉熔炼实验用钢，经过炉外精炼后浇铸成连铸坯。最后，在连铸坯相同位置取样，使用直读光谱仪（MAXX07-F）分析实验用钢的化学成分。并经过切割、研磨和抛光后，采用全自动夹杂物分析系统扫描电镜（EVO18）进行夹杂物的物相分析。
2　实验结果与分析
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2.1　钢中Ti和N元素的偏析
计算所用钢的化学成分如表1所示。
根据表1数据，计算得到相应的液相线、固相线温度分别为：
式中：Tl为液相线温度，K；Ts为固相线温度，K；Δtl（i）和△ts（i）分别为液态和固态温度因数，具体数值[11]见表2；w[i]0为溶质i的初始含量（质量分数），%。
随着钢液凝固，溶质元素扩散能力逐渐减弱。此时，可通过Ohnaka方程计算溶质i的偏析比：
式中：w[i]为溶质i在钢液凝固前沿的实际含量（质量分数），%；β[i]为逆扩散系数，cm2/s；k为溶质i的平衡分配系数；g为凝固分数。
根据表1数据：
式中：D为溶质i在固相中的扩散系数，cm2/s；RC为冷却速率，K/s。
各元素的平衡分配系数和扩散系数[12]见表3。其中R为理想气体常数，R=8.314 J/（mol·K）；T为温度，K。
根据式（1）～（4）计算钢液凝固过程中Ti和N在不同冷却速率下的偏析比，结果如图1所示。
由图1可知，在钢液凝固初、中期，Ti和N偏析较轻微。钢液凝固分数超过0.95时，Ti和N的偏析急剧增加。并且，冷却速率小于200 K/min时，Ti的偏析行为基本不随冷却速率变化而变化，但N的偏析却随着冷却速率减慢而明显增强。Ti和N的偏析行为使大量Ti和N在凝固前沿发生聚集，不可避免地析出TiN夹杂物。
2.2　TiN夹杂物析出热力学条件
TiN夹杂物析出时对应的平衡活度积KTiN为：
式中Ts-l为凝固前沿温度，K。
在凝固过程中，Ti和N因偏析发生聚集，此时，TiN的实际活度积QTiN为：
式中fTi和fN分别为Ti和N的活度系数，满足：
式中和分别为Ti和N与钢中元素之间的相互作用系数，具体数值[13]见表4。
将式（5）～（6）、式（7）～（9）分别联立，可得到N和Ti对TiN夹杂物析出热力学条件的影响，如图2所示。由图2可知，随着钢液凝固过程的推进，由于偏析作用，TiN的实际溶度积发生较大变化，当TiN的实际溶度积与平衡溶度积相等时，TiN夹杂物析出。即使钢液中Ti和N含量控制在很低的水平（Ti 0.05%，N 0.002%），仍然有TiN夹杂物析出。因此，TiN夹杂物在钢液凝固前沿析出行为是无法避免的。并且，随着Ti和N含量增加，TiN夹杂物更易析出。
图3为钢中初始N和Ti含量对钢液凝固分数的影响。由图3可以看出，钢中N和Ti任一元素含量增加都会使钢液凝固分数减小，这意味着TiN夹杂物析出时间提前。并且，对比钢液凝固分数与N和Ti含量的比值发现，N对凝固分数的减小作用约为Ti对凝固分数减小作用的10.5倍。因此，通过控制初始N含量来延缓TiN夹杂物析出时间的作用会更明显。
图4为初始N、Ti含量对TiN夹杂物析出温度的影响。由图4可见，钢中N或Ti任一元素含量增加都会使TiN夹杂物析出温度升高。因此，可以适当控制钢液中N和Ti的初始含量，从而降低TiN夹杂物析出温度，推迟TiN夹杂物的析出时间，以便减小其尺寸及析出数量。此外，从TiN析出温度对N和Ti的比值可看出，N对析出温度的影响几乎是Ti对析出温度影响的2倍，严格控制初始N含量对延迟TiN夹杂物析出时间的作用更显著。
2.3　凝固过程中TiN夹杂物的长大
TiN夹杂物析出后将进入长大过程，其半径r计算公式为：
式中：r为夹杂物半径，μm；MTiN和MFe分别为TiN和Fe的摩尔质量，kg/mol；ρTiN和ρm分别为TiN和钢液的密度，kg/m3；DN为钢液中N的扩散系数，cm2/s；w（N）e为N析出时的平衡质量分数，。
计算TiN夹杂物长大所需部分参数如表5所示。
初始N和Ti含量对TiN夹杂物尺寸的影响如图5所示。由图5可知，随着N含量增加，TiN夹杂物尺寸明显增大；而初始Ti含量对TiN夹杂物尺寸的影响很小。由此可知，降低初始N含量可有效减小TiN夹杂物的最终尺寸。
2.4　初始w（N）0×w（Ti）0积对TiN夹杂物析出的影响
为了进一步明确N和Ti含量对TiN夹杂物的析出热力学条件的影响，N含量0.005%、Ti含量0.04%～0.20%时，w（N）0×w（Ti）0积对TiN夹杂物析出的影响如图6所示。由图6可知，随着初始w（N）0×w（Ti）0积增加，凝固分数逐渐减小，TiN夹杂物越早析出。
不同w（N）0×w（Ti）0积条件下，分别计算了N含量0.002%～0.008%、Ti含量0.05%～0.20%时TiN夹杂物在凝固前沿析出时所对应的凝固分数，结果如表6所示。在所讨论范围内，w（N）0×w（Ti）0积增大，凝固分数减小，意味着TiN夹杂物越容易析出。因此，影响TiN夹杂物析出的决定性因素为w（N）0×w（Ti）0积，而非单一的Ti或N元素含量。
2.5　铸态下钢中夹杂物的显微分析
为进一步验证上文热力学的计算结果，在某钢企连铸连轧生产线试制了2批实验用钢，其具体化学成分如表7所示。
铸坯中各类夹杂物的形貌图如图7～8所示。从图7可知，1#铸坯中纯TiN夹杂物整体呈灰色，形状呈不规则多边形，边界光滑，棱角分明，存在多处尖角；TiN+氧化物/硫化物复合型夹杂物又包含两小类，一类是TiN包覆氧化物/硫化物型夹杂物，此时氧化物/硫化物夹杂物在中心，呈黑色，TiN在外层，呈灰色，同样棱角分明；另一类为氧化物/硫化物包覆TiN型夹杂物，此类夹杂物TiN在中心，氧化物/硫化物夹杂物在外层，整体呈类球形，边界较为圆润，基本没有尖角存在；氧化物/硫化物夹杂物为黑色，呈类球形。由图8可知，2#铸坯中夹杂物同样可以分为三大类，并且各类夹杂物表现出与1#铸坯基本相同的形貌特征。这意味着，钢中初始Ti和N含量由0.12%和0.005%分别减少到0.08%和0.003%时，并未改变钢中夹杂物的种类。
表8为1#、2#铸坯中夹杂物统计表，其中数密度为夹杂总数/扫描面积，平均尺寸为（所有夹杂物的平均面积×4/3.14）0.5。由表7和表8可以发现，Ti和N元素含量由0.12%和0.005%分别减小到0.08%和0.003%时，TiN夹杂物数密度由9.78个/mm2减小到7.13个/mm2，平均尺寸由6.14 μm减小到3.06 μm，分别减小了27.1%和50.2%，这充分证实了热力学计算结果。
3　结论
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1）随着冷却速度加快，N的偏析逐渐减弱，而Ti的偏析行为变化不大。并且，钢液凝固过程中Ti和N的偏析使TiN夹杂物在凝固前沿析出行为无法避免。
2）w（N）0×w（Ti）0积决定了TiN夹杂物的析出行为，且w（N）0×w（Ti）0积越大，TiN夹杂物越早析出，降低初始N含量可以减小TiN夹杂物的最终尺寸。
3）钢中初始Ti和N含量由0.12%和0.005%分别减小到0.08%和0.003%时，并未改变钢中夹杂物的种类，但使TiN夹杂物数密度和平均尺寸分别减小了27.1%和50.2%。
基金
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  • 湖南省自然科学基金(2023JJ50481)
  • 湖南人文科技学院研究生科研创新项目(ZSC2023Y37; ZSC2023Y46)
文献
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2025年第45卷第3期
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doi: 10.3969/j.issn.0253-6099.2025.03.031
  • 接收时间：2024-12-25
  • 首发时间：2026-03-19
  • 出版时间：2025-06-01
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  • 收稿日期：2024-12-25
基金
湖南省自然科学基金(2023JJ50481)
湖南人文科技学院研究生科研创新项目(ZSC2023Y37; ZSC2023Y46)
作者信息
    1.湖南人文科技学院　能源与机电工程学院，湖南　娄底　417000
    2.湖南华菱涟源钢铁有限公司，湖南　娄底　417009

通讯作者:

孔令男（1986—），男，吉林长春人，博士，副教授，主要研究方向为高强钢、耐磨钢等先进钢铁材料的组织与性能调控。Email：
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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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