1、SN中华人民共和国出入境检验检疫行业标准SN/T 0750-1999进出口碳钢、低合金钢中铝、砷、铬、钻、铜、磷、锰、钥、镍、硅、锡、钦、钒含量的测定一电感藕合等离子体原子发射光谱(ICP-AES )法Import and export carbon steel and low alloyed steel-Determination of aluminium, arsenic, chromium, cobalt, copper,phosphorus, manganese, molybdenum, nickel, silicon , tin,titanium, and vanadium cont
2、ent-Inductively coupled拟asma atomic emission spectrometric method1999一05一05发布1999一08一01实施中华人民共和国国家出入境检验检疫局发布SN/T价50-1999目次范围。、。1天准。，“，1i要，15仪器a浴欲。2。，。，。，.。，。一2精密度赶的表述，4。，。，。，。，.，一4七，尹行西9安全注意事项.4附录A(提示的附录)不同仪器测定十三种(铁基)的检出限，5附录B(提示的附录)不同型号ICP-AFS光谱仪的工作条件(参考)一5附录C(提示的附录)标准溶液的配制，.，6前言本标准是根据GB/T 1.1-1993
3、标准化工作导则第1单元:标准起草与表述规则第1部分:标准编写的基本规定的要求进行编写的。本标准遵守GB/T 1.2-1996,GB/T 1.4-1998,GB/T 1467-1978和GB/T 10725-1989各项规定。制定本标准，根据不同牌号碳钢、低合金钢中不同元素含量确定本标准的测定范围。本标准的附录A、附录B、附录C都是提示的附录。本标准由中华人民共和国国家出人境检验检疫局提出。本标准主要起草单位:中国进出口商品检验技术研究所。参加本标准研制的单位:中国进出口商品检验技术研究所、厦门商检局、天津商检局、广东商检局、广西商检局、辽宁商检局、湖南商检局、上海商检局、江苏商检局、江西商检局
4、。本标准主要起草人:孟兰香、赵国华、贺柏龄、王鸿辉、刘圣麟、汪静玲、赵恒英。中华人民共和国出入境检验检疫行业标准进出口碳钢、低合金钢中铝、砷、铬、钻、铜、磷、锰、钥、镍、硅、锡、钦、钒含量的测定一电感藕合等离子体原子发射光谱(ICP-AES )法Import and export carbon steel and low alloyed steel-Determination of aluminium, arsenic, chromiun,cobalt,copper,phosphorus， manganese, molybdenum, nickd，silicon,血，titanium, and
5、 vanadium content-Inductively coupledplasma atomic emission spectrometric methodSN/T 0750-1999范围本标准规定了电感藕合等离子体一原子发射光谱法(以下简称ICP-AES)测定碳钢，低合金钢中铝、砷、铬、钻、铜、磷、锰、铝、镍、硅、锡、钦、钒等13种元素，测定范围见表to表1 13种元素的测定范围%(m/m)元素测定范围 Al(s) As Co Cr Cu0.01一0.50 0.005一0.10 0.005一0.01 0.01一1.0 0.01一0.5元素测定范围 P Mn Mo Ni Si0.01-0.
6、05 0.011.5 0.01-0.5 0.01-0.1 0.05-0.5元素测定范围 Sn Ti v0.005-0.1 0.01-0.50 0.005-0.5(s).表示酸溶铝。2引用标准下列标准所包含的条文，通过在本标准中引用而构成为本标准的条文。本标准出版时，所示版本均为有效。所有标准都会被修订，使用本标准的各方应探讨使用下列标准最新版本的可能性。GB/T 6682-1992分析实验室用水规格和试验方法GB 10725-1989化学试剂电感藕合高频等离子体原子发射光谱法通则JJG 015-1996电感藕合等离子体原子发射光谱仪检定规程GB/T 6379-1986测试方法的精密度通过实验室
7、间试验确定标准测试方法的重复性和再现性3方法提要试样以硝酸一盐酸溶解并稀释至确定的体积后，将试样溶液喷人等离子体焰中，并以此做光源，在等离子体光谱仪相应元素波长处，测量其光谱强度。中华人民共和国国家出入境检验检疫局1999-05-05批准1999-08-01实施1SN/T 0750-19994试剂和溶液除特别声明外，本方法所用的试剂均为优级纯试剂，试验用水为去离子水均符合GB/T 6682的规定。4.1高纯铁(铁含量99.98%)04.2盐酸(p 1.19群.L).4.3硝酸(p 1.42酬.L).4.4盐酸(1+1)04.5盐酸(1+11)04.6硝酸(1+5)04.7铁基体溶液:称取5.0
8、00 0 g高纯铁(4.1)于250 mL烧杯中，加人40 mL盐酸(4.4)，盖上表面皿，低温溶解，冷却至室温。用少量水冲洗表面皿，移人100 ML容量瓶中，以去离子水稀至刻度，混匀备用。此溶液为I ML含50 mg铁。48标准溶液4.8.1 13种单元素标准溶液:单元素标准溶液可向国家认可的销售标准物质单位购买，其质量浓度为1000 mg/L(或500 mg/L).4.8.2多元素标准溶液(2倍N5):此溶液用单元素标准溶液(4.8.1)按表2计算，即分别算出相当于2倍N5的单元素标准溶液体积。按算得的体积分取13种元素单元素标准溶液(4.8.1)于200 mL容量瓶中，混匀后，用盐酸(4
9、.5)稀至200 mL，制成多元素标准溶液(2倍NS)，备用。在配制的过程中，为防止Sn的水解和Si的析出。盐酸酸度应保持在1 mol/L左右。具体配置步骤参见附录表Clo4.8.3标准系列溶液(NO一N6):分取10 ML的Fe基体溶液(4.7)于七个100 ML容量瓶中，按表2计算体积，分取计算量的2倍N5多元素标准溶液(4.8.2)于其中3个容量瓶中，并以盐酸(4.5)稀至刻度，制成标准系列N3至N5点。然后分取计算量的N4标准溶液于其中另2个容量瓶中，并以盐酸(4.5)稀至刻度制成N1一N2点。取铬、锰单元素标准溶液(4.8.1)各10 ML和硅12 mL于第六个100 ML容量瓶中，
10、并以盐酸(4.5)稀至刻度，制成标准系列N6点。第七个为NO点。在NO至N6标准系列溶液中Fe基体浓度，均为每ML含5 mg铁。具体配制步骤参见附录C2及附录C3o表2标准系列溶液(NO一N6) me/L、豪霖nr9Al As Co Cr CuM.Mo Ni P Si Sn Ti V FeNON1N2N3N4N5N60 0 0 0 0 0 0 0 0 0 0 0 0 50)0.5 0.25 0.1 0.5 0.5 0.5 0.5 0.5 0.05 0.3 0.05 0.5 0.25 50001 0.5 0.2 1 1 1 1 1 0.1 0.6 0.1 1 0.5 5 0002 1 0.4 2
11、 2 2 2 2 0.2 1.2 0忍2 1 50(D10 5 2 10 10 10 10 10 15 6 1 10 5 50(旧50 25 10 50 50 50 50 50一30 5 50 25 5000一一一100一100一一一60一一一50005仪器采用电感藕合等离子体发射光谱仪。氨气纯度应99.9%，以提供稳定清澈的等离子体炬焰。在仪器最佳工作条件下，进行测定。符合以下要求者，可以应用于本方法的测定。51仪器的稳定性5.1.1仪器短程稳定性SN/T 0750-1999在点燃等离子30 min后，进行仪器的标准化，将质量浓度约为10 mg/L的各代表元素的溶液导人等离子体炬焰中，每次曝
12、光lo s，连续测量10次，此组数据不得任意取舍或补测。用10次连续测量值的相对标准偏差(RSD)表示仪器短程稳定性。规定RSD.2.0%(见JJG 015-1996).5.1.2仪器长程稳定性的检定在点燃等离子体30 min后，进行仪器的标准化，将质量浓度约为10 m留L的各代表元素的溶液导人等离子体炬焰中，每间隔6 min测量一次，每次曝光10 s，共计测量10次，此组数据不得任意取舍或补测。用10次间隔测量值的相对标准偏差(RSD)表示仪器长程稳定性。规定RSD_4.0%(见JJG 015-1996)05.2仪器的检出限制备两种溶液:空白溶液和10倍检出限单元素溶液。在这些溶液中含有与样
13、品溶液相近的Fe基体，酸等试剂。空白溶液可用标准系列溶液NO(4.8.3)o在与被测试样溶液相同的条件下，喷人空白溶液(5.2)约10 s。读取10次强度测定数值;在同一条件下，喷人10倍检出限的溶液(5.2)约10秒中，读取10次强度测定数值。从所得强度数据，计算平均值贾1和兀及标准偏差S。计算应保留四位有效数字。以下式计算10次测定的净强度平均值Xni=X;一Xb式中:X.;净光强的平均值;X;光谱强度平均值;Xy背景光谱强度平均值。按下式计算所测元素的检出限:DL二3SC/X;这里，C是10倍检出限溶液的浓度，为mg/L.本标准测定十三种元素仪器的检出限见附录A.5.3校准(工作)曲线:
14、回归曲线的线性相关系数应Y0. 999.5.4仪器工作条件参考附录Bo6分析步骤6.1试样质量称取处理好的试样0.5000克。6.2试样份数称取两份试样进行测定，取其平均值。6.3空白试验随同试样做空白试验。6.4测定6.4.1试样的处理将试样(6.1)置于100 ML烧杯中，加人30 mL硝酸(4.6),3 mL盐酸(4.2)，放置片刻，待剧烈反应减缓后，加热溶解。当冒大气泡时，表明试样溶解充分，冷却后，移人100 ML容量瓶中，用水稀释至刻度，混均，待测。试样溶液如有碳化物沉淀，须沉静后测定清液。6.4.2校准曲线的制作按顺序测定标准系列溶液NO一N6(4.8.3)光谱强度，用计算机或计算
15、器以净光强度为因变量，以元素的浓度(W-L)为自变量进行线性回归，绘制工作曲线。计算出截距(a),斜率(b)，和线性相关系数(r)。6.4.3谱线强度的测定按实验要求及仪器规定，设置选定相应型号仪器的最佳分析条件，并调节仪器至最佳工作状态，测定空白溶液和试样溶液(6.4.1)中各待测元素的光谱强度，从工作曲线上计算出各相应组分的浓度。SN/T 0750-19997分析结果的表述按下式计算元素的百分含量:_.(C:一C.) X VW二mx 1(Yx 100式中:W被测元素的含量，%;Co从标准曲线查得的随同试样空白溶液中被测元素的浓度,pg/ML;C,从标准曲线查得的试样溶液中被测元素的浓度,V
16、岁ML;V被测试样溶液的体积,ML;m试样质量,go8精密度精密度试验原始数据经Grubbs法检验,Cochran法检验、Dixon法检验，剔除异常值后计算，本精密度数据是在1996年由10个实验室对7个水平的试样所作的试验中确定的(见表3)其中Mn的计算过程中暖为负值。根据GB/T 6379-1986的规定，令流=0，则;与R相一致。表3精密度元素1水平范围，(m/m)重复性，r再现性，*0.013一0.1800.012- 0.1090.004- 0.0130.005- 1.1720.035- 0.4200.011- 0.0550.310 - 1.5310.008- 0.6330.014 -
17、 0.1380.065一0.8050.003- 0.0360.004一0.6580.001一0.322r二0.004 5 + 0.018 3Mr = 0. 003 7 + 0.055 2Mr二0.000 4 + 0.128 1Mr二0. 002 7 + 0.093 5Mr = 0.070 7M0 Mr = 0.002 8十0.024 7Mr=0.0742+0.0172Mr = 0. 002 2 + 0.093 6Mr=0.0042+0.1106Mr二一0.000 2 + 0.125 8Mr二0.003 8+0.059 7Mr=一0.000 6 + 0.231 3Mr=0.0005+0.1026
18、MR二0.008 2+0.151 3MR二0.0194一0.030 2MR二0.004 2+0.087 2MR二0.0089一0.190 3MR二0.004 0+0.086 2MR二0.003 4+ 1.252 3MR=0.0742+0.0172MR = 0.008 1 + 0.177 9MR二。.056 3M0M aR=0.001 1+0.3144MR二0.006 2+0.010 5MR二0.005 0+0.277 9MR=0.001 2+0.278 5M尤As伪crcuPMnMoNisisn下V本方法在正常情况下，由同一操作人员，在同一实验室内，使用同一仪器，并在短期内，对同一试样所作两个
19、单次测定结果之间的差值超过重复性;平均来说20次中不多于1次。本方法在正常操作情况下，由两名操作人员，在不同实验室，对同一试样所作两个单次测定结果之间的差值超过再现性R平均来说20次中不多于1次。如果两个独立测试结果之间的差值，超过了表3中所列精密度函数关系式算出的重复性或再现性数值，则认为这两个结果是可疑的。9安全注意事项9.1应按高压钢瓶安全操作规定使用高压氢气钢瓶。9.2仪器室排风良好，等离子体炬焰中产生的废气或有毒蒸气应及时排除。9.3点燃等离子体后，应尽量少开蔽门，以防高频辐射伤害身体。9.4注意安全用电。SN/T 0750-1999附录A(提示的附录)不同仪器测定十三种元素(铁基)
20、的检出限表A1不同仪器测定十三种元素(铁基)的检出限leg/ml.仪器型号AIAsCoCrCuPMnICPV-1014(京)BAmDIS络闽)JY-70P(津)JY-70P(赣)0.0130仍50.0370.0620.0580.0230.0380.仪60.0040.0440.0420.0150.0050.0210.00670.0100.0070.0080.00470.0710.051 0.009000200.0880.013仪器型号MoNiSiSn.一，一，尸TiVICPV-1014(京)E八】日刃PS4(闽)JY-70P(津)乃-70P(赣)0.0150.0110.0590.0700.017
21、0(1冤0.0350.0310.0650.0280.0620.0150.0430.0120.0110.0060.0080.01刀0.0070.0060.0260.001 3附录B(提示的附录)不同型号ICP-AES光谱仪的工作条件(参考)表BI使用五种型号ICP-AES光谱仪的工作条件(参考)光谱仪型号岛津ICPV-1014习AI旧 PS-4IY-70PIabtsm8440-MSARL3520-AES道数焦距，M光栅刻线，条/mjn波长范围，mn线色散率倒数nm/mm多道(n+1)1工9202 160175.0-中刃0165.0- 413.70.52(1 920)0.46(2 160)多道1I
22、4)1 800173.0 - 767.0170.0一800.00.66(1440)1.1(1 800)单道(多道)13600单道(n+ m)0.75/1141 800170一8000.75单道11 080165-8000.023人射功率，kw高频功率发生器反射功率，w工作频率，MHz1299.98%)4.2 Hydrochloric acid4.3 Nitric acid4.4 Hydrochloric acid (1+1)4.5 Hydrochloric acid (1+11)4.6 Nitric acid (1+5)4.7 Iron matrix solution:Weigh 5.000
23、0 g of high purity iron (4.1),put it in a beaker of 250 mL.Add 40 mL of hydrochloric acid (4.4) in the beaker, then cover it with watch glass and slightlyheat it till iron is completely solved, cool it at the room temperature. Wash the watch glass with asmall amount of water.Transfer the solution in
24、to a measuring flask of 100 mL and dilute it with de-ionized water until the graduation, mix it homogeneously for reserve.The concentration of this so-toSN/T 0750-1999lution of iron is 50 mg/mL.4.8 Standard solution4.8.1 Single element standard solution for 13 elements: Every single element standard
25、 solutioncan be purchased from selling standard substance unit approved by the State. Its mass concentra-tion is 1 000 mg/mL (or 500 mg/mL).4.8.2 Multielement standard solution (two times N5): the solution is prepared with the single el-ement standard solution (4.8.1) according to Table 2., namely,s
26、eparetly, calculate the single ele-ment standard solution volume corresponded to two times N5. Separetly take the single elementstandard solution for 13 elements (4.8.1) according to the calculated volume and put it in mea-suring flask of 200 mL,dilute it to 200 mL with hydrochloric acid (4.5), prep
27、are multielement stan-dard solution (two times N5) for reserve. In the process of preparation, the concentration of hy-drochloric acid should be kept in about 1 mol/L preventing the tin hydrolysis and the silicon sepa-rating out.4.8.3 Series standard solutions (N0- N6):separatly take 10 mL of iron m
28、atrix solution and putin seven measuring flasks. Calculate the volumes according to Table 2. Separately take two timescalculated volume of N5 (4.8.2) multielement standard solution and put it in three measuringflasks of seven flasks, dilute it with hydrochloric acid (4.5) until graduation, prepare s
29、eries stan-dard solutions from N3 to N5. Then separately take calculated volume of N4 standard solution andput it in another two measuring flasks, dilute it with hydrochloric acid (4.5) until graduation andprepare N1 and N2. Separately take 10 mL of chromium and manganese single element standardsolu
30、tion and 12 mL of silicon, put it in the sixth measuring flask and dilute it with hydrochloric acid(4.5) until graduation, prepare N6 of series standard solution. The seventh flask solution is NO.The every iron matrix concentration of series standard solutions from NO to N6 is 5 mg/mL.Thepractical p
31、rocedure of preparation can be seen in annex C.Table 2 Series mixture standard solutions (NON6)mg/LElementAI As Co Cr Cu Mn Mo Ni P Si Sn Ti V FeNON1N2N3N4N5N60 0 0 0 0 0 0 0 0 0 0 0 0 50000.5 0.25 0.1 0.5 0.5 0.5 0.5 0.5 0.05 0.3 0.05 0.5 0.25 5 0001 0.5 0.2 1 1 1 1 1 0.1 0.6 0.1 1 0.5 5 0002 1 0.4
32、 2 2 2 2 2 0.2 1.2 0.2 2 1 5 00010 5 2 10 10 10 10 10 15 6 1 10 5 500050 25 10 50 50 50 50 50一30 5 50 25 5000一一一1a)一100一一一60一一一5 0005 ApparatusThe inductively coupled plasma atomic emission spectrogroph is used. The argon gas used inSN/T 0750-1999this experiment has to be pure enough(99.9%) for gett
33、ing a stable and clear plasma torchflame.The determination can be done on the best working condition of the apparatus.This mehtodcan be used for determination, according with the requirements as following.5.1 Stability of instrument5.1.1 Short-term stabilityThe apparatus has been standardizing after
34、 30 min, when the plasma was lighted. The everyrepresentative element solution with mass concentration of 10 mg/L was introduced into plasmatorch flame. It was exposed once 10 s and continuously determined ten times. The wanton accep-tance and rejection or additional determination of this group of d
35、ata were not allowed. The short-term stability of the apparatus was expressed by the relative standard deviation (RSD) for tentimes continuous determination. It was provided that RSD 2.0% or RSD=2.0% (see JJG 015-1996).5.1.2 Examination and determination of the long-term stability of the apparatusTh
36、e apparatus has been standardizing after 30 min, when the plasma was lighted. The everyrepresentative element solution with mass concentration of 10 mg/L was introduced into plasmatorch flame. It was determined once at intervals of six minutes and exposed once 10 s. It was total-ly determined ten ti
37、mes. The wanton acceptance and rejection or additional determination of thisgroup of data were not allowed.The long-term stability of the apparatus was expressed by the rel-ative standard deviation (RSD) for ten times discontinuous determination. It was provided thatRSD4.0% or RSD=4.0% (see JJG 015-
38、1996).5.2 Detection limit of instrumentPrepare two solutions: blank solution and ten times detection limit single element solution.The iron matrix, acid and other reagent content of these solutions and sample solution is similar.NO of the series standard solution (4.8.3) can be used as blank solutio
39、n.Spray blank solution (5.2) about 10 s on condition every experiment parameter is identicalwith that for determined sample solution. Take the data for ten times intensity determination. Onthe same conditions, spray ten times detection limit single element solution (5.2) about 10 s, takethe data for
40、 ten times intensity determination. Caculate average values X, Xb,and standard devi-ation S. Calculation has to keep, four significant digits. Caculate average value of net intensity forten times determination by following formula.Xi二X,一XbIn the formula, Xi-average value of net intensity;Xi the mean
41、 of spectral intensity;Xb the mean of background spectral intensity.Calculate the detection limit of the determined element by following formula:DL =3SclxniHere C is the concentration of ten times detection limit solution (mg/L).12SN/T 0750=1999The detection limit of the apparatus for 13 determined
42、elements can be seen in annex A.5.3 Correction (working) curve: linear correlation coefficient of regression curve (r) is 0.999.5.4 Working conditions (see annex B)6 Procedure of analysisSample mass weigh 0.5 g of treated sample with accuracy 0.000 1 g.Sample portionsweigh and determine duplicate sa
43、mples,take its mean.，.nZ:666.3 Blank test blank test was finished with the sample.6.4 Determination6.4.1 Sample treatmentPut the sample (6.1) into the 100 mL-beaker,add 30 mL of nitric acid (4.6) and 3 mL of hy-drochloric acid (4.2).Wait a moment,when the sample is completely dissolved and cool,tran
44、sferthe solution into the 100 ml-measuring flask, dilute it with water to 100 mL graduation, homoge-neously mix it and reserve it for determination. If there is some carbonide sediment in the samplesolution, use the clear liquor after complete precipitation.6.4.2 The making of correction curveDetermine the spectral intensities of the series standard s
