Article(id=1198266575846470125, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, articleNumber=1009-5438(2023)02-0095-04, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1658160000000, receivedDateStr=2022-07-19, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1763618614398, onlineDateStr=2025-11-20, pubDate=1682352000000, pubDateStr=2023-04-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763618614398, onlineIssueDateStr=2025-11-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763618614398, creator=13701087609, updateTime=1763618614398, updator=13701087609, issue=Issue{id=1198266568997175650, tenantId=1146029695717560320, journalId=1185652524569653253, year='2023', volume='49', issue='2', 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=1763618612765, creator=13701087609, updateTime=1763619383107, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1198269800108618470, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1198269800108618471, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1198266568997175650, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=95, endPage=98, ext={EN=ArticleExt(id=1198266576119099886, articleId=1198266575846470125, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Determination of Boron in Low-alloy Steel with Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and Multispectral Fitting Analysis Technology, columnId=1187102804364640261, journalTitle=Science & Technology of Baotou Steel, columnName=Others, runingTitle=null, highlight=null, articleAbstract=

In this paper, the boron in low-alloy steel is determined with ICP-AES and multispectral fitting analysis technology. The analytical spectral lines of elements, interference and correction of coexistence elements as well as detection limits are studied by the condition experiments with instrument. The measuring range is determined to be 0.001%~0.100%. With the method, samples are dissolved with the mixed acid of hydrochloric acid and nitric acid, then they are directly determined with instrument. As a result, a simple and rapid analysis method for determining boron content in low-alloy steel is established, which is with good accuracy and precision.

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文章利用电感耦合等离子体原子发射光谱法(ICP-AES),采用多谱线拟合分析技术测定低合金钢中的硼,经仪器条件试验对元素分析谱线、共存元素干扰及校正、检出限等进行研究,确定测定范围为0.001%~0.100%。该方法采用盐酸硝酸混合酸分解试样后,利用仪器直接进行测定,建立了一种简单和快速测定低合金钢中硼含量的分析方法,具有良好的精密度和准确度。

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刘钢耀(1973-),男,内蒙古包头市人,高级工程师,现从事冶金材料化学分析研究工作。

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刘钢耀(1973-),男,内蒙古包头市人,高级工程师,现从事冶金材料化学分析研究工作。

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刘钢耀(1973-),男,内蒙古包头市人,高级工程师,现从事冶金材料化学分析研究工作。

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figureFileSmall=null, figureFileBig=null, tableContent=
射频发生器功率/W 冷却气流量/(L·min-1) 辅助气流量/(L·min-1) 雾化器压力/kPa 蠕动泵提升量/(mL·min-1)
1 300 15 0.2 128 1.5
), ArticleFig(id=1198266578572767798, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=CN, label=表1, caption=

工作参数表

, figureFileSmall=null, figureFileBig=null, tableContent=
射频发生器功率/W 冷却气流量/(L·min-1) 辅助气流量/(L·min-1) 雾化器压力/kPa 蠕动泵提升量/(mL·min-1)
1 300 15 0.2 128 1.5
), ArticleFig(id=1198266578631488056, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
元素 分析谱线/nm 共存元素干扰
B 249.677 铁的249.653 nm特征谱线与之部分重叠
B 249.772 铁的249.772 nm特征谱线与之全部重叠
B 208.957 铁的208.950 nm特征谱线与之全部重叠
), ArticleFig(id=1198266578694402618, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=CN, label=表2, caption=

元素分析谱线与共存元素干扰

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元素 分析谱线/nm 共存元素干扰
B 249.677 铁的249.653 nm特征谱线与之部分重叠
B 249.772 铁的249.772 nm特征谱线与之全部重叠
B 208.957 铁的208.950 nm特征谱线与之全部重叠
), ArticleFig(id=1198266578744734268, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
元素 波长/nm MFS校正前工作
曲线相关系数(r)
MFS校正后工作
曲线相关系数(r)
B 249.677 0.954 62 0.999 20
B 249.772 0.965 64 0.999 45
B 208.957 0.998 06 0.999 96
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MFS校正前和校正后工作曲线校正系数对照

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元素 波长/nm MFS校正前工作
曲线相关系数(r)
MFS校正后工作
曲线相关系数(r)
B 249.677 0.954 62 0.999 20
B 249.772 0.965 64 0.999 45
B 208.957 0.998 06 0.999 96
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样品编号 波长/nm 校正前/% 绝对误差/% 校正后/% 绝对误差/% 标准值/%
GBW01326 249.677
249.772
208.957
0.005 2
0.003 6
0.001 0
0.003 6
0.002 0
0.000 6
0.001 4
0.001 4
0.001 5
0.000 2
0.000 2
0.000 1
0.001 6
GBW01325 249.677
249.772
208.957
0.004 7
0.002 7
0.003 1
0.001 0
0.001 0
0.000 6
0.001 6
0.001 6
0.003 4
0.002 1
0.002 1
0.000 3
0.003 7
MnCrCuB 249.677
249.772
208.957
0.004 0
0.003 6
0.002 8
0.000 7
0.001 1
0.001 9
0.002 4
0.002 4
0.005 0
0.002 3
0.002 3
0.000 3
0.004 7
GBW01308 249.677
249.772
208.957
0.017
0.015
0.012
0.001
0.001
0.004
0.012
0.012
0.017
0.004
0.004
0.001
0.016
GBW01312 249.677
249.772
208.957
0.021
0.021
0.021
0.007
0.007
0.007
0.025
0.025
0.027
0.003
0.003
0.001
0.028
YSBC18207-94 249.677
249.772
208.957
0.005 2
0.008 3
0.006 6
0.002 5
0.000 6
0.001 1
0.005 5
0.005 5
0.007 4
0.002 2
0.002 2
0.000 3
0.007 7
), ArticleFig(id=1198266578971226689, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=CN, label=表4, caption=

校正前和后测定结果比较

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样品编号 波长/nm 校正前/% 绝对误差/% 校正后/% 绝对误差/% 标准值/%
GBW01326 249.677
249.772
208.957
0.005 2
0.003 6
0.001 0
0.003 6
0.002 0
0.000 6
0.001 4
0.001 4
0.001 5
0.000 2
0.000 2
0.000 1
0.001 6
GBW01325 249.677
249.772
208.957
0.004 7
0.002 7
0.003 1
0.001 0
0.001 0
0.000 6
0.001 6
0.001 6
0.003 4
0.002 1
0.002 1
0.000 3
0.003 7
MnCrCuB 249.677
249.772
208.957
0.004 0
0.003 6
0.002 8
0.000 7
0.001 1
0.001 9
0.002 4
0.002 4
0.005 0
0.002 3
0.002 3
0.000 3
0.004 7
GBW01308 249.677
249.772
208.957
0.017
0.015
0.012
0.001
0.001
0.004
0.012
0.012
0.017
0.004
0.004
0.001
0.016
GBW01312 249.677
249.772
208.957
0.021
0.021
0.021
0.007
0.007
0.007
0.025
0.025
0.027
0.003
0.003
0.001
0.028
YSBC18207-94 249.677
249.772
208.957
0.005 2
0.008 3
0.006 6
0.002 5
0.000 6
0.001 1
0.005 5
0.005 5
0.007 4
0.002 2
0.002 2
0.000 3
0.007 7
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检测限 测定下限 加入量 测定值 回收率
0.000 1 0.001 0 0.100 0.102 102
), ArticleFig(id=1198266579118027333, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=CN, label=表5, caption=

元素检出限和测定范围%

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检测限 测定下限 加入量 测定值 回收率
0.000 1 0.001 0 0.100 0.102 102
), ArticleFig(id=1198266579193524807, tenantId=1146029695717560320, journalId=1185652524569653253, articleId=1198266575846470125, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
标准样品号 测定值 平均值 标准值 标准偏差 相对标准偏差
钢GBW01325 0.003 9,0.004 0,0.003 9,0.003 9,0.003 8,
0.003 7,0.003 6,0.003 9,0.003 9,0.004 0
0.003 8 0.003 7 0.000 13 3.42
钢GBW01312 0.026,0.029,0.028,0.027,0.027,0.029,
0.027,0.028,0.026,0.027
0.027 0.028 0.001 2 4.81
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准确度及精密度%

, figureFileSmall=null, figureFileBig=null, tableContent=
标准样品号 测定值 平均值 标准值 标准偏差 相对标准偏差
钢GBW01325 0.003 9,0.004 0,0.003 9,0.003 9,0.003 8,
0.003 7,0.003 6,0.003 9,0.003 9,0.004 0
0.003 8 0.003 7 0.000 13 3.42
钢GBW01312 0.026,0.029,0.028,0.027,0.027,0.029,
0.027,0.028,0.026,0.027
0.027 0.028 0.001 2 4.81
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ICP-AES利用多谱拟合测定低合金钢中硼
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刘钢耀 , 薛玉兰 , 王宴秋 , 常欢
包钢科技 | 其他 2023,49(2): 95-98
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包钢科技 | 其他 2023, 49(2): 95-98
ICP-AES利用多谱拟合测定低合金钢中硼
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刘钢耀, 薛玉兰, 王宴秋, 常欢
作者信息
  • 内蒙古包钢钢联股份有限公司技术中心,内蒙古 包头 014010
  • 刘钢耀(1973-),男,内蒙古包头市人,高级工程师,现从事冶金材料化学分析研究工作。

Determination of Boron in Low-alloy Steel with Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and Multispectral Fitting Analysis Technology
Gang-yao Liu, Yu-lan Xue, Yan-qiu Wang, Huan Chang
Affiliations
  • Technical Center of Inner Mongolia Baotou Steel Union Co. , Ltd. , Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2023-04-25
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文章利用电感耦合等离子体原子发射光谱法(ICP-AES),采用多谱线拟合分析技术测定低合金钢中的硼,经仪器条件试验对元素分析谱线、共存元素干扰及校正、检出限等进行研究,确定测定范围为0.001%~0.100%。该方法采用盐酸硝酸混合酸分解试样后,利用仪器直接进行测定,建立了一种简单和快速测定低合金钢中硼含量的分析方法,具有良好的精密度和准确度。

ICP-AES法  /  低合金钢  /  多谱拟合  /  硼

In this paper, the boron in low-alloy steel is determined with ICP-AES and multispectral fitting analysis technology. The analytical spectral lines of elements, interference and correction of coexistence elements as well as detection limits are studied by the condition experiments with instrument. The measuring range is determined to be 0.001%~0.100%. With the method, samples are dissolved with the mixed acid of hydrochloric acid and nitric acid, then they are directly determined with instrument. As a result, a simple and rapid analysis method for determining boron content in low-alloy steel is established, which is with good accuracy and precision.

ICP-AES  /  low-alloy steel  /  multispectral fitting  /  boron
刘钢耀, 薛玉兰, 王宴秋, 常欢. ICP-AES利用多谱拟合测定低合金钢中硼. 包钢科技, 2023 , 49 (2) : 95 -98 .
Gang-yao Liu, Yu-lan Xue, Yan-qiu Wang, Huan Chang. Determination of Boron in Low-alloy Steel with Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and Multispectral Fitting Analysis Technology[J]. Science & Technology of Baotou Steel, 2023 , 49 (2) : 95 -98 .
硼被誉为钢中的维生素,其含量甚微也能对钢质起到很大的影响,能成倍地增加钢淬透性是其最独特的作用。同时,硼又能增加钢的硬度和抗张力,改善钢的焊接性能[1]。因此,准确、快速地测定钢中硼含量,对冶炼工艺等研究起着非常重要的作用。测定微量硼的方法有甲醇蒸馏-姜黄素光度法GB/T 223.75—91[2]、次甲基蓝-二氯乙烷萃取光度法和新硼试剂(HPTA)光度法,传统的化学分析方法操作繁琐,分析速度慢,难以满足现代冶金分析和材料研究的需要。随着仪器分析的发展,国家标准GB/T 228.81—2007采用微波消解技术处理样品,利用电感耦合等离子体质谱法测定钢铁及合金中的总铝含量和总硼含量。该方法联合使用微波消解仪和等离子体质谱仪完成硼含量的测定,但由于分析设备成本较高,许多分析实验室按照检测标准无法开展工作。本文采用盐酸和硝酸混合酸溶解样品后,利用电感耦合等离子体发射光谱仪,采用多谱拟合技术可以准确快速地测定样品中的硼含量。经过研究,采用5300DV等离子体光谱仪利用多谱拟合技术完全可以解决光谱干扰问题,极大地提高了标准工作曲线的工作相关系数,实现钢铁材料中硼含量简便、准确、快速的测定。
Optima 5300DV全谱直读等离子发射光谱仪(美国PE公司)。
硼标准储备液:1.0 mg/mL,称取2.858 0 g硼酸(基准纯)于250 mL烧杯中,用水溶解,移入500 mL容量瓶中,用水稀释至刻度,摇匀。
盐酸:ρ约为1.19 g/mL,优级纯。
硝酸:ρ约为1.42 g/mL,优级纯。
高氯酸:ρ约为1.72 g/mL,优级纯。
高纯铁:质量分数不小于99.5%,硼质量分数小于0.000 5%。
美国PE公司生产Optima 5300DV双向观测型全谱直读等离子光谱仪,采用固体检测器(CCD),波长范围165~780 nm,中阶梯光栅,进样系统采用宝石十字交叉雾化器和Scoton雾室,具体工作参数见表1
称取0.5 g试样(精确至0.000 1 g)于150 mL石英烧杯中,加入20 mL盐酸硝酸混合酸(1+1+2)于低温电热板加热溶解试样,然后加入3 mL高氯酸,加热至冒烟3~5 min,取下,冷却,加入10 mL盐酸硝混合酸(1+1+2)于低温电热板加热溶解盐类,冷却,转移定容至100 mL聚乙烯容量瓶中。待仪器稳定后将试液引入ICP光源,按照仪器分析程序进行硼含量的测定。
分别称取0.5 g高纯铁(精确至0.000 1 g)六份于150 mL石英烧杯中,按1.3试验方法溶解样品,转移至100 mL聚乙烯容量瓶中,加入硼标液制成含硼0、0.002%、0.005%、0.010%、0.050%、0.100%标准溶液系列,按照仪器设定的工作条件待仪器稳定后,采用多谱拟合模式以各元素浓度为横坐标、发射强度为纵坐标绘制工作曲线。
根据仪器主要推荐分析谱线对含1 μg/mL硼标准溶液、主要共存元素铁及可能存在的共存元素硅、锰、磷、铬、镍、铜、钒、钛、钼、铝、镁、砷、锑、铋、锡、铅、汞、锌、钨等进行光谱扫描。光谱干扰见表2
通过光谱干扰试验发现基体元素铁对硼分析特征谱线存在严重干扰现象,影响分析检测结果。因此需要通过多谱拟合法(MSF)来校正其光谱干扰问题。多谱拟合法是采集主体元素、干扰元素和分析元素的光谱轮廓线,由此推算出拟合的各自数学模型,再从采集到的实际样品光谱分析信号中,扣除由数学模型推算出基体及干扰元素造成的干扰背景,从而获得分析元素的净强度信号。为此,通过对空白溶液、含有单一元素硼的溶液与基体元素铁进行光谱扫描,建立多谱拟合(MSF)模式对测定元素进行分析,通过多谱拟合技术消除铁的特征谱线对硼的特征谱线造成的光谱干扰。
分别称取0.500 0 g高纯铁六份于150 mL石英烧杯中,按1.3试验方法溶解样品,转移至100 mL聚乙烯容量瓶中,加入硼标液制成含硼0、0.002%、0.005%、0.010%、0.050%、0.100%标准溶液系列,按照仪器设定的工作条件待仪器稳定后,以各元素浓度为横坐标、发射强度为纵坐标,分别采用多谱拟合模式和不采用多谱拟合模式绘制工作曲线。
通过对MFS校正前和校正后工作曲线相关系数对照(见表3),可以明显看出较正后的工作曲线相关系数可以提高1~2个数量级。
按照1.3溶解样品,通过对空白溶液、硼标液及铁干扰组分进行光谱扫描,建立多谱拟合(MSF)模式和非多谱拟合模式对硼进行分析,试验结果见表4
表4结果表明,分别采用硼249.677 nm、249.772 nm、208.957 nm三条特征谱线进行分析时,由于受到铁基体干扰,不采取多谱拟合技术和利用多谱拟合技术分析前后测定结果变化较大,即使利用多谱拟合技术,利用硼的不同特征谱线进行测定,其结果准确度还是有很大差异。表4结果显示采用208.957 nm特征谱线利用多谱拟合技术测定硼的结果更加准确,因此,选择硼208.957 nm作为多谱拟合特征谱线进行钢中硼含量的测定。
以铁基体打底制作的空白标准溶液,同时测定空白溶液11次,标准偏差3倍为检出限,检出限10倍为测定下限。加入硼含量0.100%的硼标液和0.5 g的铁基体按照1.3方法进行样品处理后,经测定硼的回收率在95%~105%,确定测定范围为0.001%~0.100%,结果见表5
按试验方法对低合金钢标准样品中硼含量进行10次独立测定,该方法的相对标准偏差(RSD)均小于5%,测定值与标准值相吻合,具有较好的精密度和准确度,结果见表6
通过利用多谱拟合技术开发了等离子体发射光谱仪的检测功能,解决了硼的特征分析谱线受铁特征谱线干扰的影响,提高了工作曲线相关系数。具有简便、快速分析的优点,分析结果具有良好的精密度和准确度,能满足日常分析检测需求。
参考文献 引证文献
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[1]
鞍钢钢铁研究所, 沈阳钢铁研究所. 实用冶金分析方法与基础[M]. 沈阳: 辽宁科学技术出版社, 1990.
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GB/T 223.75—91,钢铁及合金化学分析方法:甲醇蒸馏-姜黄素光度法[S].
2023年第49卷第2期
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  • 接收时间:2022-07-19
  • 首发时间:2025-11-20
  • 出版时间:2023-04-25
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  • 收稿日期:2022-07-19
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    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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