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Article(id=1188423626102555550, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1188423621174244026, articleNumber=1009-5438(2024)03-0036-09, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1712505600000, receivedDateStr=2024-04-08, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1761271872306, onlineDateStr=2025-10-24, pubDate=1719244800000, pubDateStr=2024-06-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1761271872306, onlineIssueDateStr=2025-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1761271872306, creator=13701087609, updateTime=1761271872306, updator=13701087609, issue=Issue{id=1188423621174244026, tenantId=1146029695717560320, journalId=1185652524569653253, year='2024', volume='50', issue='3', pageStart='1', pageEnd='98', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=0, articleOrder=1, issueType=-1, specialIssue=null, createTime=1761271871131, creator=13701087609, updateTime=1761283363050, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1188471821818015773, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1188423621174244026, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1188471821818015774, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1188423621174244026, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=36, endPage=44, ext={EN=ArticleExt(id=1188423626295493537, articleId=1188423626102555550, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Effects of Rare Earth Elements on Performances of Refining Slag, columnId=1188423622092796608, journalTitle=Science & Technology of Baotou Steel, columnName=Production Practices and Mlanagement, runingTitle=null, highlight=null, articleAbstract=

The effects of refining slag on cleanliness of liquid steel are very important. Its main functions are improving the deoxidizing capacity of deoxidizing elements, absorbing nonmetallic inclusions in steel and preventing secondary oxidation of liquid steel to generate FeO, MnO and SiO2. In the process of refining liquid steel, the reasonable composition of refining slag plays a role of adsorbing and removing inclusions in steel. In the process of smelting rare earth steel, rare earth oxides and rare earth sulfides are formed due to rare earth is easy to react with oxygen and sulfur elements in steel as well as rare earth elements could enter refining slag because of the function of potential energy of high oxygen and sulfur for refining slag. In the production process of steelmaking, the contents of each component in ternary refining slag CaO-SiO2-Al2O3 are different and the effects of rare earth on physical properties of refining slag are different because of different deoxidation systems. In the paper, such physical properties of rare earth refining slag when smelting rare earth steel as melting point, viscosity and alkalinity are analyzed by means of testing to predict the physical properties of refining slag, which could provide theoretical basis for improving the level of slag formation, cleanliness of smelting steel grade and yield of rare earth.

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精炼渣对钢液洁净度有着非常重要的影响,其作用主要有提高脱氧元素的脱氧能力、吸收钢中的非金属夹杂物和防止钢液的二次氧化生成FeO、MnO和SiO2。钢液精炼过程中,合理的精炼渣成分起到了吸附去除钢中夹杂物的作用。在稀土钢冶炼过程中,因稀土易与钢中氧、硫元素发生反应,并且由于精炼渣高氧、高硫势能的作用,稀土元素会进入精炼渣中,形成稀土氧化物、稀土硫化物。炼钢生产过程中因不同的脱氧制度,三元精炼渣CaO-SiO2-Al2O3中各组分含量不同,稀土对精炼渣物理性能影响也会有所差异。文章通过测试的手段对稀土钢冶炼时稀土精炼渣熔点、黏度、碱度等物理性质进行了分析,以预测精炼渣的物理性质,对提高造渣水平及冶炼钢种洁净度、提高稀土收得率提供理论依据。

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张 胤(1985-),男,河北省张家口市人,工程师,现从事炼钢工艺研究工作。

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张 胤(1985-),男,河北省张家口市人,工程师,现从事炼钢工艺研究工作。

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张 胤(1985-),男,河北省张家口市人,工程师,现从事炼钢工艺研究工作。

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化学成分(质量分数)/% R R+RE
F CaO MnO TiO2 S MgO SiO2 TFe FeO P2O5 Ce Al2O3
1.31 52.7 0.16 0.48 1.03 7.6 20.08 0.76 0.69 <0.050 0.2 15.03 2.62 2.63
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铝脱氧钢精炼离位渣样

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化学成分(质量分数)/% R R+RE
F CaO MnO TiO2 S MgO SiO2 TFe FeO P2O5 Ce Al2O3
1.31 52.7 0.16 0.48 1.03 7.6 20.08 0.76 0.69 <0.050 0.2 15.03 2.62 2.63
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化学成分(质量分数)/% R R+RE
CaO MnO TiO2 S MgO SiO2 TFe P2O5 Ce Al2O3
52.4 0.32 0.41 0.4 6.87 25.55 0.55 0.5 0.23 5.33 2.05 2.06
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无铝脱氧钢精炼离位渣样

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化学成分(质量分数)/% R R+RE
CaO MnO TiO2 S MgO SiO2 TFe P2O5 Ce Al2O3
52.4 0.32 0.41 0.4 6.87 25.55 0.55 0.5 0.23 5.33 2.05 2.06
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渣样 CaO Al2O3 SiO2 Ce MgO
1 50.07 19.54 18.52 0.10 7.95
2 48.04 15.84 20.32 0.21 7.76
3 50.69 18.91 21.42 0.31 7.63
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铝脱氧精炼渣系成分(质量分数) %

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渣样 CaO Al2O3 SiO2 Ce MgO
1 50.07 19.54 18.52 0.10 7.95
2 48.04 15.84 20.32 0.21 7.76
3 50.69 18.91 21.42 0.31 7.63
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渣样 CaO Al2O3 SiO2 Ce MgO
1 57.40 3.31 27.48 0.10 7.73
2 50.08 2.82 27.58 0.20 7.94
3 51.40 2.70 27.36 0.32 7.91
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无铝脱氧精炼渣系成分(质量分数) %

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渣样 CaO Al2O3 SiO2 Ce MgO
1 57.40 3.31 27.48 0.10 7.73
2 50.08 2.82 27.58 0.20 7.94
3 51.40 2.70 27.36 0.32 7.91
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Ce含量/% 试验温度/℃ 平均温度/℃
0.103 1 373 1 378 1 375 1 375
0.209 1 398 1 406 1 407 1 404
0.311 1 389 1 393 1 392 1 391
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铝脱氧钢精炼渣熔化温度

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Ce含量/% 试验温度/℃ 平均温度/℃
0.103 1 373 1 378 1 375 1 375
0.209 1 398 1 406 1 407 1 404
0.311 1 389 1 393 1 392 1 391
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Ce含量/% 试验温度/℃ 平均温度/℃
0.100 1 462 1 466 1 467 1 465
0.195 1 472 1 472 1 475 1 473
0.318 1 481 1 482 1 486 1 483
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无铝脱氧钢精炼渣熔化温度

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Ce含量/% 试验温度/℃ 平均温度/℃
0.100 1 462 1 466 1 467 1 465
0.195 1 472 1 472 1 475 1 473
0.318 1 481 1 482 1 486 1 483
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Ce含量/% 黏度/(Pa·s) CaO/Al2O3
1 500 ℃ 1 520 ℃ 1 540 ℃ 1 560 ℃ 1 580 ℃ 1 600 ℃
0.103 2.25 2.01 1.79 1.60 1.44 1.29 2.8
0.209 1.74 1.56 1.40 1.25 1.13 1.02 2.5
0.311 1.93 1.72 1.54 1.38 1.24 1.12 2.6
0 2.40 2.13 1.90 1.70 1.52 1.37 5.5
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铝脱氧钢精炼渣黏度

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Ce含量/% 黏度/(Pa·s) CaO/Al2O3
1 500 ℃ 1 520 ℃ 1 540 ℃ 1 560 ℃ 1 580 ℃ 1 600 ℃
0.103 2.25 2.01 1.79 1.60 1.44 1.29 2.8
0.209 1.74 1.56 1.40 1.25 1.13 1.02 2.5
0.311 1.93 1.72 1.54 1.38 1.24 1.12 2.6
0 2.40 2.13 1.90 1.70 1.52 1.37 5.5
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Ce含量/% 黏度/(Pa·s) CaO/Al2O3
1 500 ℃ 1 520 ℃ 1 540 ℃ 1 560 ℃ 1 580 ℃ 1 600 ℃
0.11 1.29 1.16 1.04 0.94 0.85 0.78 16.67
0.23 1.12 1.01 0.91 0.82 0.75 0.68 12.14
0.29 1.55 1.39 1.25 1.13 1.02 0.93 7.68
1.45 1.30 1.17 1.06 0.96 0.87 12.03
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无铝脱氧钢精炼渣黏度

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Ce含量/% 黏度/(Pa·s) CaO/Al2O3
1 500 ℃ 1 520 ℃ 1 540 ℃ 1 560 ℃ 1 580 ℃ 1 600 ℃
0.11 1.29 1.16 1.04 0.94 0.85 0.78 16.67
0.23 1.12 1.01 0.91 0.82 0.75 0.68 12.14
0.29 1.55 1.39 1.25 1.13 1.02 0.93 7.68
1.45 1.30 1.17 1.06 0.96 0.87 12.03
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稀土元素对精炼渣性能的影响
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张胤 1, 2 , 张怀军 1, 2 , 刁望才 1, 2 , 张顺 3 , 曹瑞峰 3 , 韩春鹏 1, 2
包钢科技 | 生产实践与管理 2024,50(3): 36-44
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包钢科技 | 生产实践与管理 2024, 50(3): 36-44
稀土元素对精炼渣性能的影响
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张胤1, 2, 张怀军1, 2, 刁望才1, 2, 张顺3, 曹瑞峰3, 韩春鹏1, 2
作者信息
  • 1.内蒙古包钢钢联股份有限公司技术中心, 内蒙古 包头 014010
  • 2.内蒙古自治区稀土钢产品研发企业重点实验室, 内蒙古 包头 014010
  • 3.内蒙古包钢钢联股份有限公司炼钢厂, 内蒙古 包头 014010

    • 张 胤(1985-),男,河北省张家口市人,工程师,现从事炼钢工艺研究工作。

Effects of Rare Earth Elements on Performances of Refining Slag
Yin Zhang1, 2, Huai-jun Zhang1, 2, Wang-cai Diao1, 2, Shun Zhang3, Rui-feng Cao3, Chun-peng Han1, 2
Affiliations
  • 1. Technical Center of Inner Mongolia Baotou Steel Union Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
  • 2. Inner Mongolia Key Laboratory of Rare Earth Steel Products Research & Development, Baotou 014010, Inner Mongolia Autonomous Region, China
  • 3. Steel-making Plant of Inner Mongolia Baotou Steel Union Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2024-06-25
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摘要
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精炼渣对钢液洁净度有着非常重要的影响,其作用主要有提高脱氧元素的脱氧能力、吸收钢中的非金属夹杂物和防止钢液的二次氧化生成FeO、MnO和SiO2。钢液精炼过程中,合理的精炼渣成分起到了吸附去除钢中夹杂物的作用。在稀土钢冶炼过程中,因稀土易与钢中氧、硫元素发生反应,并且由于精炼渣高氧、高硫势能的作用,稀土元素会进入精炼渣中,形成稀土氧化物、稀土硫化物。炼钢生产过程中因不同的脱氧制度,三元精炼渣CaO-SiO2-Al2O3中各组分含量不同,稀土对精炼渣物理性能影响也会有所差异。文章通过测试的手段对稀土钢冶炼时稀土精炼渣熔点、黏度、碱度等物理性质进行了分析,以预测精炼渣的物理性质,对提高造渣水平及冶炼钢种洁净度、提高稀土收得率提供理论依据。

稀土  /  精炼渣  /  收得率

The effects of refining slag on cleanliness of liquid steel are very important. Its main functions are improving the deoxidizing capacity of deoxidizing elements, absorbing nonmetallic inclusions in steel and preventing secondary oxidation of liquid steel to generate FeO, MnO and SiO2. In the process of refining liquid steel, the reasonable composition of refining slag plays a role of adsorbing and removing inclusions in steel. In the process of smelting rare earth steel, rare earth oxides and rare earth sulfides are formed due to rare earth is easy to react with oxygen and sulfur elements in steel as well as rare earth elements could enter refining slag because of the function of potential energy of high oxygen and sulfur for refining slag. In the production process of steelmaking, the contents of each component in ternary refining slag CaO-SiO2-Al2O3 are different and the effects of rare earth on physical properties of refining slag are different because of different deoxidation systems. In the paper, such physical properties of rare earth refining slag when smelting rare earth steel as melting point, viscosity and alkalinity are analyzed by means of testing to predict the physical properties of refining slag, which could provide theoretical basis for improving the level of slag formation, cleanliness of smelting steel grade and yield of rare earth.

rare earth  /  refining slag  /  yield
张胤, 张怀军, 刁望才, 张顺, 曹瑞峰, 韩春鹏. 稀土元素对精炼渣性能的影响. 包钢科技, 2024 , 50 (3) : 36 -44 .
Yin Zhang, Huai-jun Zhang, Wang-cai Diao, Shun Zhang, Rui-feng Cao, Chun-peng Han. Effects of Rare Earth Elements on Performances of Refining Slag[J]. Science & Technology of Baotou Steel, 2024 , 50 (3) : 36 -44 .
正文
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精炼渣的熔点、黏度、碱度直接影响炉外精炼工序的生产顺行程度,并且这三项指标对精炼去除钢水中夹杂物也有重要影响。精炼渣成分和碱度对钢中夹杂物尺寸能起到一定的控制作用,当精炼渣碱度适当时有利于钢中细小夹杂物的形成[1]。目前,CaO-Al2O3是常用的精炼渣系,具有熔点低、精炼渣黏度小、流动性好、成渣时间短的优点。在稀土钢精炼过程中,不可避免会出现稀土氧化物的传质过程,包括夹杂物的上浮和扩散,生成的氧化物夹杂物对精炼渣的性能有一定的影响。研究发现[2-7],精炼渣中加入稀土氧化物后,能够很好地吸附Al2O3夹杂物,脱氧率和夹杂物级别降低率均能达到15%以上,能够有效地提高精炼效率。但是,稀土氧化物的加入对于精炼渣熔化性能的影响仍不明确[8]。
在稀土钢冶炼过程中,随精炼过程进行,精炼渣中富集大量氧、硫元素,在稀土铈合金加入过程中,合金最先与精炼渣接触,并进入钢包钢液-精炼渣层界面,在氧、硫作用下,活泼的稀土元素会率先与氧、硫结合后形成铈氧化物、铈硫化物,随钢包底吹氩气的搅拌作用,氩气泡携带夹杂物一起上升至钢渣界面,在夹杂物自身的浮力和钢液运动的作用下被渣层捕捉,并受精炼渣吸附作用进入到精炼渣中,从而达到去除钢液中夹杂物的目的[9]。随稀土元素与CaO-SiO2-Al2O3体系精炼渣中各元素反应以及夹杂物的捕捉富集,精炼渣表面张力、渣金间界面张力随精炼渣成分变化而变化。
对比锰、硅、铝、铈等元素氧化物标准生成吉布斯自由能[10],在稀土钢冶炼过程中,因稀土的特殊性质以及精炼渣高氧、高硫势能的作用,稀土元素会进入精炼渣中,形成稀土氧化物、稀土硫化物。Clarence E Sims 和Charles W Briggs[11]在研究中认为稀土(RE)不适合作为脱氧剂和脱硫剂,主要是提高硫饱和度,降低硫偏析。在传统三元精炼渣CaO-SiO2-Al2O3以及四元精炼渣CaO-SiO2-MgO-Al2O3研究中,只对基础三元或四元精炼渣共存理论进行了研究。稀土元素作为特殊元素,只在冶炼稀土钢时加入,影响精炼渣黏度、熔点、熔速等物理性质的关键因素在于精炼渣中Al2O3及CaO含量。研究表明[12-14],调整精炼渣中Al2O3活度并提高精炼渣流动性可改善精炼渣对Al2O3夹杂物的吸收。为了降低渣中Al2O3的活度,可以采取控制精炼渣成分的方法,如增加渣中CaO含量等。然而CaO含量增加会升高精炼渣碱度并使得Al2O3含量降低,导致渣的流动性变差,从而不利于夹杂物吸收。因此,改进精炼渣系的冶金性能以便精炼渣能更好的吸收Al2O3类夹杂物成为国内冶金行业重点研究课题[15-16]。
包头拥有丰富的稀土资源,随稀土在钢中应用研究的推广,稀土资源在钢铁行业应用具有广阔的前景。研究表明,Ce2O3与Al2O3相比偏碱性[17],能与Al2O3结合形成CexOy-Al2O3类化合物,降低Al2O3在精炼渣中的活度[18]。随Al2O3含量的变化,精炼渣物理性能也发生改变。目前,稀土氧化物对连铸结晶器内保护渣性能的影响已有相关研究[19-20]。而基于不同脱氧制度下精炼渣中Al2O3、SiO2含量不同,在稀土含量增加的情况下,应当考虑稀土对不同脱氧制度下精炼渣物理性能的影响。本文针对两种渣系展开相应研究。
1 理论基础
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根据CaO-SiO2-Al2O3三元相图,精炼渣熔化温度随着精炼渣中Al2O3含量在有限范围内的提高而降低。当CaO、SiO2、Al2O3在渣中的含量分别为50%~60%、10%~20%、30%~40%时,随着渣中Al2O3含量的提高,渣中CaO和Al2O3生成低熔点的铝钙酸盐物质(CaO·Al2O3),其熔化温度只有1 510 ℃左右。因此,精炼渣中Al2O3含量的提高,可以促进化渣,实现快速造渣。富含Al2O3的还原渣中,含有铝酸钙,铝酸钙熔点低,对钢液的粘附力较大,能迅速从钢液中浮出;且铝酸钙被硫化钙很好的润湿,一起从钢液中浮出,保证了钢液的洁净度。在CaO-SiO2-Al2O3三元渣系中,精炼渣的表面张力随SiO2含量提高而降低,随着Al2O3含量的提高而提高,从而使得精炼渣吸附夹杂物的能力增强,钢中夹杂物含量降低。精炼渣Al2O3含量主要影响精炼渣熔点、熔速,对精炼渣黏度的影响相对较小。
精炼渣的黏度、密度和表面张力等物性参数对精炼渣泡沫化程度有重要影响。所以埋弧精炼渣不仅要有良好的精炼能力,同时还必须具备合适的黏度、密度和表面张力等物理性质以满足精炼渣泡沫化的要求。精炼渣起泡指数与精炼渣黏度成正比,与表面张力和密度的平方根成反比。精炼渣的碱度和CaF2含量对起泡指数有较大影响,而Al2O3含量对起泡指数影响很小。CaO含量提高,精炼渣碱度高时,熔渣的表面张力增加,熔渣的发泡高度和保持时间都会相应减小,而CaF2含量低时,熔渣的表面张力降低,熔渣的发泡高度和保持时间都会相应增加。精炼渣CaO含量主要影响精炼渣碱度,从而对精炼渣黏度产生影响[21]。
2 稀土精炼渣岩相
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岩相检测结果如图1、图2所示。铝脱氧以及无铝脱氧两种不同脱氧制度下精炼渣组成、岩相基本相同,主要由镁蔷薇辉石、硅酸二钙和玻璃相等矿物组成。硅酸二钙呈粒状,褐色,粒径在50~100 μm;镁蔷薇辉石也呈粒状,色浅,可见菱形轮廓,粒径在25~50 μm;金属铁较多(白色圆点),粒径5~10 μm;未找到典型稀土化合物。
利用扫描电镜对两种脱氧制度下精炼离位渣样进行分析,结果如图3所示。
在扫描电镜观测区域,选取不同形态岩相组织进行成分分析,均未能检测到稀土元素。XRD分析精炼渣成分,检测稀土元素存在状态,如图4所示。
由XRD分析结果可知,稀土元素在精炼渣中以氧化铈、硫化铈、氧硫化铈的形式存在。氧化铈以两种形式留存于渣样中,即CeO2、Ce7O12。通过渣样XRD分析,稀土与渣中氧、硫接触后,形成相应化合物并组成复合化合物。
3 稀土含量对精炼渣性能影响
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3.1 稀土含量对精炼渣碱度影响
分析稀土对无铝脱氧、铝脱氧两种精炼渣碱度的影响。对于CaO-SiO2-MgO-Al2O3-RE系精炼渣(铝脱氧钢种),取样对精炼渣进行了分析检测。选取工位为LF离位前,加入稀土铈铁合金后,精炼渣组分平均含量如表1所示。精炼渣平均碱度为2.62,因稀土元素属于弱碱性,计算碱度时,以CaO、Ce含量的和计算三元碱度,用R+RE表示,平均碱度R+RE为2.63,对不加稀土生产铝脱氧钢种渣样进行分析,平均碱度为2.74,稀土加入对精炼渣碱度影响不大。
对于CaO-SiO2-MgO-Al2O3-RE系精炼渣(无铝脱氧钢种),取样对精炼渣进行了分析检测。选取工位为LF离位前,加入稀土铈铁合金后,精炼渣组分平均含量如表2所示。精炼渣平均碱度为2.05,平均碱度R+RE为2.06,对不加稀土生产无铝脱氧钢种渣样进行分析,平均碱度为2.01,稀土加入对精炼渣碱度影响不大。
在工业生产条件下,虽然精炼渣中稀土含量较高(平均在0.3%),且稀土氧化物呈弱碱性,但对无铝脱氧、铝脱氧两种精炼渣碱度影响不大。其原因在于精炼渣碱度主要依靠CaO与SiO2比值,稀土氧化物含量相较于CaO含量对精炼渣影响可忽略不计。
3.2 稀土含量对精炼渣熔化温度影响
对无铝脱氧、铝脱氧两种不同脱氧制度的精炼渣成分进行试验,检验稀土含量对精炼渣熔点、熔速等物理性质的影响。选取两种脱氧制度下稀土钢冶炼精炼渣,精炼渣中CaO、SiO2、MgO、Al2O3、Ce成分以混合后精炼渣检验值为准。选取的精炼渣的目标成分见表3和表4。
两种脱氧制度下精炼渣成分中,稀土含量基本相同,精炼渣MgO含量、CaO含量基本相同,只在Al2O3、SiO2含量不同。根据理论,Al2O3含量影响精炼渣熔点、熔速,而CaO含量影响精炼渣黏度。使用FactSage软件对铝脱氧、无铝脱氧精炼渣进行分析,如图5和图6所示。
从三元相图中标记的等温线及精炼渣成分位置分析可知,在铝脱氧精炼渣及无铝脱氧精炼渣中加入稀土后,精炼渣成分趋向于高熔点区域。
对铝脱氧钢渣系进行成分活度计算,1 300~1 600 ℃区间内发现含稀土精炼渣中稀土铝酸盐、稀土铝酸钙等物质活度较高,而不含稀土精炼渣中,单纯铝酸盐、铝酸钙盐活度较高。从计算分析中可以发现,加入稀土后,稀土Ce与精炼渣中CaO、Al2O3形成稀土化合物,改变了精炼渣各组分活度结构,这一现象在XRD衍射分析中也可得到印证。含稀土精炼渣中,稀土铝酸钙类物质居多。精炼渣各组分的改变,影响活度系数,从而影响低熔点铝酸钙盐析出的热力学条件。检测结果如表5所示。
对无铝脱氧钢渣系进行成分活度计算,1 300~1 600 ℃区间内发现含稀土精炼渣中稀土硅酸盐、稀土硅铝酸钙等物质活度较高,而不含稀土精炼渣中,单纯铝酸钙、硅铝酸钙活度较高。从计算分析中可以发现,由于精炼渣中Al2O3含量较低,加入稀土后,稀土Ce与精炼渣中CaO、Al2O3形成稀土化合物,改变了精炼渣各组分活度。无铝脱氧精炼渣中Al2O3含量低,形成低熔点钙铝酸盐活度相对较窄,稀土加入更易改变精炼渣各组分的活度系数,从而影响低熔点铝酸钙析出的热力学条件。检测结果如表6所示。
综合对两种脱氧制度精炼渣熔化温度的实际测量值发现,铈含量对铝脱氧钢精炼渣的熔化温度有较大影响,当铈含量从0.103%增加到0.209%时,熔化温度提高29 ℃,从而会对精炼渣熔化效果带来不利影响;而铈含量对无铝脱氧钢精炼渣的熔化温度也产生影响。从FactSage计算中也可以看出,含稀土铝脱氧钢、无铝脱氧钢精炼渣熔点右移至高熔点位置。因此,在稀土钢生产时,应适当考虑稀土合金加入后精炼渣中稀土含量,以便提高和优化精炼渣熔化性。
3.3 稀土含量对精炼渣黏度影响
精炼温度下较低的黏度值是精炼渣具有良好流动性的一个重要标志,同时黏度随温度变化的敏感性对实际精炼过程也起着重要作用。对含铈铝脱氧钢精炼渣的黏度进行测量,分析了其高温下的黏度及黏度随温度变化情况,并与目前常用的精炼渣进行比较。表7为各试样1 500~1 600 ℃时的黏度检测结果。
将1 500~1 600 ℃时含稀土铝脱氧精炼渣的黏度分布范围与不含稀土铝脱氧精炼渣的黏度相比较,含稀土精炼渣的黏度分布范围为1.02~2.25 Pa·s,不含稀土精炼渣黏度分布范围在1.37~2.40 Pa·s内,说明精炼渣中添加适量的铈均能获得良好的精炼渣高温流动性。图7为铝脱氧不同稀土含量下精炼渣黏度。
对含铈无铝脱氧钢精炼渣的黏度进行测量,分析其高温下的黏度及黏度随温度变化,并与目前常用的精炼渣进行比较。表8为各试样1 500~1 600 ℃时的黏度检测结果。
将1 500~1 600 ℃时含稀土无铝脱氧精炼渣的黏度分布范围与不含稀土无铝脱氧精炼渣的黏度相比较,含稀土精炼渣的黏度分布范围为0.68~1.55 Pa·s,不含稀土精炼渣黏度分布范围在0.87~1.45 Pa·s内,说明精炼渣中添加适量的铈均能获得良好的精炼渣高温流动性。图8为无铝脱氧不同稀土含量下精炼渣黏度。
4 结论
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(1)稀土元素在精炼渣中以化合物形式存在,因精炼渣高氧、高硫势能同时稀土具有活泼的化学性质,稀土首先形成稀土氧化物、稀土硫化物及稀土氧硫化物,在精炼过程中,随稀土化合物与精炼渣中各组分进行相互界面反应,受精炼渣组分活度的影响,稀土化合物会在精炼渣中形成稀土硅酸盐、稀土铝酸盐等化合物。
(2)Ce含量对铝脱氧精炼渣的熔化温度有较大影响,当Ce含量从0.103%增加到0.209%时,熔化温度提高29 ℃;Ce含量对无铝脱氧钢精炼渣的熔化温度也会产生影响,但相对影响较小。
(3)对于铝脱氧钢精炼渣,精炼渣中稀土含量不同,稀土与精炼渣中CaO、Al2O3形成相应稀土铝酸盐、稀土钙化物,从而影响精炼渣中CaO与Al2O3结合比例,增加高熔点铝酸钙产生量,导致精炼渣表面张力增加,因此精炼渣在相同温度下,高温流动性下降,精炼渣黏度增加;对于无铝脱氧钢精炼渣,Ce含量达到0.3%时,Ce与CaO、SiO2形成稀土硅酸钙类物质,改变了CaO在精炼渣中活度,从而增加精炼渣中低熔点7Al2O3·2CaO生成量,导致精炼渣表面张力降低,黏度因此下降;而Ce含量在0.2%时,硅酸钙量不足以影响CaO与Al2O3结合比例,对精炼渣表面张力影响不大,因此黏度与不含稀土精炼渣黏度基本相同;而Ce含量在0.1%时,CaO与Al2O3反应易生成的高熔点铝酸钙,增加了精炼渣表面张力,因此CaO/Al2O3值升高,精炼渣黏度值下降。
(4)在LF生产过程中,精炼渣在精炼末期主要作用为软吹期间吸附上浮夹杂物,而精炼渣黏度对夹杂物吸附能力会产生影响。可通过精炼过程加入稀土,调整精炼渣黏度,增强精炼渣对夹杂物吸附能力。
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    1.内蒙古包钢钢联股份有限公司技术中心, 内蒙古 包头 014010
    2.内蒙古自治区稀土钢产品研发企业重点实验室, 内蒙古 包头 014010
    3.内蒙古包钢钢联股份有限公司炼钢厂, 内蒙古 包头 014010
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2种不同金属材料的力学参数
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Family		 属数
Number of
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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
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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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