XRF谱仪在水泥原材料分析中的应用

1、xrf谱仪在水泥原材料分析中的应用吉昂分析原料、生料、熟料和成品中的主要成份有nao、mgo、al2o3、sio2、so3、cao、fe2o3，有时还要分析cl及痕量元素等。国外早在二十年前就对水泥中tl、pb、cd、cr、zn等痕量元素的分析给予重够的重视12。基于生产水泥时有时使用工业废渣或旧轮胎等，痕量及有害元素的分析就显得十分重要。 xrf谱仪 以panalytical为例 wdxrf： magix、cubix、venus200 edxrf： minipal，minimatetaiheiyos ofunato 工厂用pw2606谱仪进行常规分析，pw2404做痕量元素分析。大连日本小野

2、田用magix对常规和痕量元素同时进行分析。 基础知识可参考 1.x射线荧光光谱分析 吉昂 陶光仪 卓尚军 罗立强 编箸，中国科学院研究教材丛书，科学出版社，2003年 2.能量色散x射线荧光光谱分析 曹利国 成都科技大学出版社，1998年 本文就分析对象、基体校正、能量色散和波长色散谱仪在分析分析中应用等方面作简单介绍。 分析对象主要成份有nao、mgo、al2o3、sio2、so3、cao、fe2o3，有时还要分析cl。水泥中待分析微量元素含量范围及检测限 (ppm)magixlldv4.5cr3.1ni0.6cu1.2zn1.6as0.8sr1.1zr2.0mo3.0cd2.0ba8.3

3、pb1.7tl0.3最小值324510122202.022040100.6140301最大值240226802051200404201861103069050010基体效应1、元素间相互影响当用足够高的电压如50kv激发样品时，可以使样品中存在的元素均可产生相应的特征x射线，即x射线荧光。这些特征x射线可以是k系线，也可能是l系线。水泥中经常要分析的元素的吸收限能量和特征x射线能量列于表1。 表1. 水泥中经常要分析的元素的吸收限能量和特征x射线能量待分析元素fnamgalsiskcafek系吸收限(kev)0.6871.081.3031.5591.8372.4703.6064.0377.10

4、1k线能量(kev)0.6771.041.2541.4871.7402.3073.3113.6906.400 试样中的元素均可吸收所发射的特征x射线，这种吸收有光电吸收和散射吸收两种，当待测元素的特征x射线的能量大于基体中某一元素的k系吸收限，就可激发该元素，使之产生二次x射线荧光.1、元素间相互影响 a、从表1看元素间存在吸收增强效应，z+1元素均可激发z元素，现以xrf分析专用系列水泥生料(gsb 08-1110-1999)为对象用magix分析结果为例说明问题。al2o3philips analyticalcalibration details for al2o3 in rm道: alm

5、atrix model:classic模式:c=d+e.r.m比例道:背景:1standards:10d:-0.52642e:0.12049f:0rms:0.0356k:0.01947指数校正:标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)(%)(%)s12.0962.14 -0.0440522.798621.7636s22.3832.380.0028425.287624.1446s42.8972.860.037429.7228.415s53.1453.110.0345731.843330.4663s63.3493.340.0093133.68232.1655s

6、73.6323.590.0421836.124134.5131s83.8263.83 -0.0036137.846436.1249s94.054.07 -0.0196239.725937.9839s104.3054.31 -0.0045141.984640.1011s114.4924.55 -0.0575443.530841.6528al2o3 of wsbsio2分析结果#philips analyticalcalibration details for sio2 in rm道: simatrix model:classic模式:c=d+e.r.m背景:1standards:10d:1.92

7、592e:0.11053f:0rms:0.06675k:0.01808标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)(%)(%)(%)s111.05111.13 -0.0792182.80482.556s211.64311.65 -0.0065888.162887.9178s412.76912.710.0587198.395298.0987s513.33713.250.08679 103.5393 103.2383s613.7313.77 -0.04044 107.1153 106.7918s714.39714.30.09684 113.1805112.829s

8、814.84414.830.01425 117.2378 116.8768s915.32215.35 -0.02846 121.5425121.195s1015.85815.89-0.0316 126.4337 126.0522s1116.33716.41 -0.07292130.746130.383cao分析结果#philips analyticalcalibration details for cao in rm道: camatrix model:classic模式:c=d+e.r.m比例道:背景:1standards:10d:10.31542e:0.06743f:0rms:0.05609

9、k:0.00869标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)(%)(%)(%)s1139.09739.060.03734 435.1688 426.8523s1039.66639.660.00629 443.8702 435.2902s940.3240.270.04964 453.7178 444.9798s840.88540.870.01471 462.2035453.36s741.34641.48-0.134 469.2388 460.2013s642.05242.08 -0.02781 479.7955 470.6745s542.67242.68 -0

10、.00844489.239479.86s443.30543.290.0154 498.8127 489.2602s244.50144.50.00139516.92 506.9975s145.14545.10.04486526.716 516.5405结论 以粉末压片法分析gsb 08-1110-1999标样的校正曲线表明：在该标样的浓度范围内，直接用实验校正法制定校正曲线时，其rms、k 和校正曲线值与标样值均满足质量控制要求。 结果表明：生料的元素间吸收增强效应可以忽略。2、颗粒度效应颗粒度效应 从上图可以看出，颗粒度效应有两方面： 颗粒大小，即粒径; 颗粒均匀性。颗粒度影响 生料粉碎时间与

11、强度的关系粉碎时间(s)mgalsikcafe901.81753.385563.12611.176222.2593.3351801.82743.277764.361411.2186218.6593.4282401.83453.220564.391411.2133218.44553.43133001.83213.176464.582611.2285217.97393.4964300:901.00800.93821.0231.00470.98071.048240:1801.00390.98241.00051.00050.99901.0096 增加研磨时间，并不只是减少平均粒径，而是可以更小的颗粒填

12、允两个较大的颗粒间的空隙，密度增加，使样品表面更平。 逃逸深度相对于颗粒大小是相当小的情况，阴影效应阴影效应(shadow effect)是有意义的，反之如果逃逸深度是大的，则楔入效应楔入效应(wedge effect)是有意义的。3、矿物结构效应 生料是由石灰石、粘土、粉砂岩或砂岩、硫酸渣及煤灰等和铁矿石等混合而成，所分析的元素与这几种矿物的来源和矿物结构效应有关。石灰石是水泥配料中主要成分，约占总量的80%左右，我国目前水泥厂使用的石灰岩，按地质年代分从寒武系到三叠系；按石灰岩成因区分，既有沉积岩，又有变质岩；按化学成分cao的含量 55.2%到30.0%。矿物结构效应 矿物相结构矿物相结

13、构差异引起 2 位移和元素在不同相中质量吸收系数的差异，使强度产生变化。以gsb 08-1110-1999标样和工厂实际参比样为对象来说明该问题矿物效应引起2 角度的变化al2o3-1al2o3-2al2o3-3al2o3-4不同矿物来源配制的生料中cao分析philips analyticalcalibration details for cao in rmstandards:19d:14.74522e:0.05728rms:0.48156k:0.07326standard measurement dateex.c(calc)c(chem)diff(c)gross rate net rate

14、 lld (tb = 100 s)(%)(%)(%)(kcps)(kcps)(ppm)s11#39.19339.060.13342 435.1688 426.852323.684s10#39.67739.660.01671 443.8702 435.290223.881s9#40.23240.27 -0.03831 453.7178 444.979823.904s8#40.71240.87 -0.15833 462.2035453.3623.885s7#41.10441.48 -0.37649 469.2388 460.201324.016y6#42.21541.550.66501489.06

15、 479.607524.205s6#41.70342.08 -0.37664 479.7955 470.674523.934y8#42.86742.230.63708 500.5488 490.992324.14y7#42.86742.340.52686 500.6105 490.988524.223s5#42.22942.68 -0.45053489.239479.8624.106y5#43.3842.910.46987 509.8023 499.945324.366y4#43.24942.940.30895 507.3695 497.659524.221y2#43.06343.08 -0.

16、01667 504.1482 494.418724.3y3#43.65243.10.55194 514.7245 504.695524.499y1#43.5343.140.3901 512.3468 502.568324.226s4#42.76843.29 -0.52213 498.8127 489.260224.165s3#43.52443.89 -0.36625 512.2143 502.457324.201s2#43.78444.5 -0.71621516.92 506.997524.331s1#44.3345.1 -0.76963526.716 516.540524.486不同矿物来源

17、配制的生料中cao分析经验系数校正不同矿物来源配制的生料中cao分析经验系数校正不同矿物来源配制的生料中sio2分析philips analyticalcalibration details for al2o3 in rm道: almatrix model:classic模式:c=d+e.r.m比例道:背景:1standards:18d:-0.62156e:0.1106f:0rms:0.44475k:0.25202标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)(%)(%)(%)s11.7852.14 -0.3545522.798621.7636y12.5362.

18、290.2459129.912528.549s22.0492.38 -0.3312125.287624.1446y52.8932.460.4326533.230631.7746y72.8262.470.3558932.63731.171y32.8142.490.3238132.511731.0617y83.0392.560.4787334.628933.0954y22.8492.570.2793232.879331.3828y43.0772.570.5065334.972733.4372y63.2042.650.5543636.144534.593s42.5212.86 -0.3389129.

19、7228.415s52.7483.11 -0.3620431.843330.4663s62.9363.34 -0.4041233.68232.1655s73.1963.59 -0.3944836.124134.5131s83.3743.83 -0.4562137.846436.1249s93.5794.07 -0.4906139.725937.9839s103.8144.31 -0.4964541.984640.1011s113.9854.55 -0.5648443.530841.6528不同矿物来源配制的生料中fe2o3分析philips analyticalcalibration deta

20、ils for fe2o3 in rm道: fematrix model:classic模式:c=d+e.r.m比例道:背景:1standards:18d:0.02636e:0.04708f:0rms:0.18558k:0.12321标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)基体(%)(%)(%)s111.5831.370.2126233.418233.0562s101.8091.610.1991238.230837.8673s92.0381.860.1775643.06442.7195s82.32.10.1999448.640348.2928y11.956

21、2.12 -0.1643941.341840.9788y72.1382.3 -0.1624545.23144.8435s72.5012.350.1507752.940552.5585y22.1722.35 -0.1784945.948345.5648y32.1712.39-0.218745.928345.5603y42.2572.48 -0.2231847.753347.3768y62.3032.49 -0.1868848.740848.3603y82.2882.5 -0.2116748.436248.0462y52.2492.51 -0.2605447.605547.2205s62.7212

22、.60.1211657.616357.2398s52.9622.840.1224562.76162.365s43.1753.090.0848167.266366.8758s23.6333.580.0530477.01576.609s13.8623.820.0419581.8653 用国标生料分析山东东源生料结果 样品号sio2al2o3fe2o3caomgoy1化学值13.122.292.1243.142.13xrf13.212.911.7644.202.00+0.09+0.62-0.361.060.13y2化学值13.262.572.3543.081.93xrf13.973.251.9954

23、3.651.98+0.71+0.68-0.3550.570.05y3化学值13.312.492.3943.101.82xrf13.053.221.2644.341.75-0.26+0.73-1.131.240.07y4化学值13.502.572.4842.941.86xrf13.723.502.0943.871.76+0.22+0.93-0.390.930.10y5化学值13.592.462.5142.911.80xrf13.423.302.0844.021.77-0.17+0.84-0.431.110.03y6化学值14.302.652.4941.552.55xrf14.783.642.14

24、42.662.44+0.48+0.99-0.351.110.11y7化学值13.712.472.3042.342.34xrf13.933.231.9643.422.22+0.22+0.76-0.341.080.12y8化学值13.942.562.5042.232.17xrf14.043.462.1243.422.12+0.10+0.90-0.381.190.05结论：1、从上表可见，分析的生料与实际生产样的组份相近，如sio2的含量范围从13.12%14.30%，al2o3的含量范围从2.29%3.65%，fe2o3的含量范围从2.12%2.50%，cao的含量范围从1.55%43.14%。但

25、sio2的分析绝对差的变化从-0.26%到0.48%；al2o3分析绝对差的变化从0.62%到0.93%；fe2o3分析绝对差的变化从-0.34%到-1.13%；cao分析绝对差的变化从0.57%到1.19%；mgo的含量范围从.13%2.55%，分析绝对差的变化在允许误差范围内。2、sio2、al2o3、fe2o3和cao的分析绝对差来看，若用其中任何一个样的xrf测定值与化学分析值之间的绝对差去修正d值，除al2o3的误差为0.30%外，其它元素均超差。结论 矿物效应和颗粒度效应矿物效应和颗粒度效应是生料分析结果误差主要来源； 以改变截距使 曲线平移的方法校正矿物效应和颗粒度效应有时虽然可

26、行，但数据在很大程度上不可信。 粉末压片法的问题很复杂，无论在理论上还是实践上均不是简单的，在目前要予以解释是很困难的。如何解决颗粒度和矿物效应用熔融法，在时间上是能满足要求的；但可获得最准确的结果；使用粉末压片法，需在标样与试样诸矿物相匹配的情况下，并有足够的数量。用经验系数法对所测元素进行校正亦可获得可用于生产质量控制的结果。数学校正方法1.sio2的校正philips analyticalcalibration details for sio2 in rmchannel: simatrix model:classicmodel:c=d+e.r.mratio channel:backgro

27、unds:1standards:19d:9.613e:0.36345rms:0.13497k:0.03651coefficientvaluelocksourcealpha for sio20 lockedmanualalpha for al2o3-0.6322 unlocked regressionalpha for cao-2.0091 unlocked regressionalpha for mgo-1.2475 unlocked regressionstandard c(calc)c(chem)diff(c)gross rate net rate matrix(%)(%)(%)(kcps

28、)(kcps)s111.72111.130.5909382.80482.5560.07025s212.09111.650.440988.162887.91780.07755s312.23112.190.0411585.076384.83130.08492s412.90112.710.1906798.395298.09870.09221y113.03913.12-0.0815102.521 102.20550.09222s513.35213.250.10177 103.5393 103.23830.09964y213.34513.260.08504109.39 109.06850.09415y3

29、13.11413.31 -0.19612 101.0253 100.73330.09562y413.40913.5 -0.09114 107.0758 106.75380.09783y513.3913.59 -0.19976104.361 104.05350.09988y713.74213.710.03185 108.9765 108.67750.10453s613.76613.77 -0.00399 107.1153 106.79180.107y813.92913.94 -0.01122109.959 109.65150.10829s714.29714.3 -0.00269 113.1805

30、112.8290.11423y614.54814.30.24767 116.7453 116.39830.11665s814.77814.83 -0.05156 117.2378 116.87680.1216s915.29115.35 -0.05943 121.5425121.1950.12889s1015.86115.89 -0.02853 126.4337 126.05220.13639s1116.42216.410.0118130.746130.3830.143682.al2o3的校正philips analyticalcalibration details for al2o3 in r

31、m道: almatrix model:classic模式:c=d+e.r.m背景:1standards:18d:0.5199e:0.55642f:0rms:0.0407k:0.02396系数数值锁住来源alpha for al2o34.4187 解锁的回归alpha for cao-1.3694 解锁的回归beta for sio2-3.1259 解锁的回归标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)基体(%)(%)(%)s12.1712.140.0309222.798621.76360.13634y12.2592.29 -0.0307829.912528.5

32、490.10949s22.4022.380.0218325.287624.14460.14008y52.4022.46 -0.0575233.230631.77460.10648y72.4472.47 -0.0230232.63731.1710.11111y32.4882.49 -0.0021232.511731.06170.11386y82.5452.56 -0.0154134.628933.09540.10995y22.6072.570.0368732.879331.38280.11951y42.6432.570.0730834.972733.43720.11412y62.6882.650

33、.0381536.144534.5930.11265s42.8492.86 -0.0110729.7228.4150.14731s53.0843.11 -0.0257131.843330.46630.15127s63.2913.34 -0.0492533.68232.16550.15482s73.5753.59 -0.0149236.124134.51310.15909s83.7983.83 -0.0318437.846436.12490.16309s94.0564.07-0.013739.725937.98390.16732s104.3394.310.0290241.984640.10110

34、.17116s114.5884.550.0380143.530841.65280.175533.cao的校正philips analyticalcalibration details for cao in rm道: camatrix model:classic模式:c=d+e.r.m比例道:背景:1standards:18d:31.75794e:0.04453f:0rms:0.11826k:0.01814系数数值锁住来源alpha for sio2-3.718 解锁的回归标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)基体(%)(%)(%)s1139.16939.

35、060.1088 435.1688 426.85230.38988s1039.6939.660.03006 443.8702 435.29020.40921s940.26440.27 -0.00553 453.7178 444.97980.42929s840.81540.87 -0.05501 462.2035453.360.44862s741.35641.48-0.1245 469.2388 460.20130.46833y641.7641.550.21021489.06 479.60750.46833s641.98742.08 -0.09307 479.7955 470.67450.488

36、03y842.2942.230.0603 500.5488 490.99230.48171y742.47742.340.13719 500.6105 490.98850.49026s542.642.68-0.0803489.239479.860.50736y542.77242.91 -0.13794 509.8023 499.94530.49472y442.79642.94 -0.14414 507.3695 497.65950.49807y242.9243.08 -0.15956 504.1482 494.41870.50699y343.11143.10.01068 514.7245 504

37、.69550.50513y143.22143.140.08093 512.3468 502.56830.5122s443.2543.29 -0.04049 498.8127 489.26020.52744s244.55644.50.05591516.92 506.99750.56685s145.24245.10.14152526.716 516.54050.586194.fe2o3的校正#philips analyticalcalibration details for fe2o3 in rm道: fematrix model:classic模式:c=d+e.r.m比例道:背景:1standa

38、rds:18d:0.73209e:0.09989rms:0.14801k:0.09441系数数值锁住来源alpha for fe2o3-3.357 解锁的回归beta for sio2-4.3768 解锁的回归标样c(计算)c(化学)diff(c)毛计数率(kcps)净计数率(kcps)基体(%)(%)(%)s111.5431.370.1726333.418233.05620.24548s101.7211.610.1111838.230837.86730.2615s91.9181.860.0582843.06442.71950.27799s82.1492.10.0491848.640348.2

39、9280.29377y12.2322.120.1123141.341840.97880.36652y72.2382.3 -0.0619145.23144.84350.33622s72.3572.350.0074352.940552.55850.3096y22.3442.35 -0.0064345.948345.56480.35407y32.3292.39 -0.0614245.928345.56030.35081y42.3422.48-0.138147.753347.37680.34018y62.2092.49 -0.2810748.740848.36030.30573y82.2722.5 -

40、0.2282148.436248.04620.32083y52.3152.51 -0.1954947.605547.22050.3355s62.5922.6-0.00857.616357.23980.3253s52.8552.840.0147562.76162.3650.34075s43.1143.090.0244967.266366.87580.35665s23.6983.580.1176477.01576.6090.38755s14.0083.820.1879581.865381.47130.40255熔融法要有材质为5%au95%pt的铂金坩埚及模具，高温炉最高温度不得低于12000c，

41、熔剂有无水四硼酸锂、偏硼酸锂及其混合物，如a12(66%li2b4o7+34%libo2)熔剂。 用a12熔剂与试样比例建议使用表2中所推荐的方法。表4中所用熔融时间应根据熔融设备确定，若熔融设备无搅拌功能，应人工将熔融体摇动三次以上，保证熔融体均匀，浇铸前，模具加热至红，浇铸后，冷却温度应根据试样选择，保证玻璃片透明、无折晶。 熔剂98%li2b4o7+2%nai。0.700克样+7.00克熔剂。7000c预热5分钟，加热至11500c熔 融，共20m。自然冷却。不同矿物的熔融法条件 表4熔融方法的制样条件样品名称试样与熔剂比氧化剂预氧化温度熔融温度水泥和白云岩1.8:91克nh4no500

42、度1分钟1100度4分钟黏土和高岑土1.8:8同上同上1100度5分钟砂岩和土址1:8,1份li2co3 1100度6分钟矿1.8:8,1份li2co32克nh4no3200度预热3分钟1100度7分钟矿渣1.8:8,1份li2co31克nh4no3500度预热2分钟1100度5分钟矿渣，含硫1.8克样加10ml硝酸,8克熔剂,1克li2co3 200度预热3分钟，500度预热2分钟1100度5分钟铝土矿1.8:8,1份li2co31克nh4no3500度预热2分钟1100度3.5分钟石膏1.8:8,1份li2co31克nh4no3500度预热1分钟1100度3.5分钟生料1.8:8,1份li2co31克nh4no3500度预热2分钟1100度3.5分钟熟料1:8,1份li2co31克nh4no3500度预热1分钟1100度4分钟