XRF譜儀在水泥原料分析中的應(yīng)用

1、xrf譜儀在水泥原材料分析中的應(yīng)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，有時(shí)還要分析cl及痕量元素等。國(guó)外早在二十年前就對(duì)水泥中tl、pb、cd、cr、zn等痕量元素的分析給予重夠的重視12?；谏a(chǎn)水泥時(shí)有時(shí)使用工業(yè)廢渣或舊輪胎等，痕量及有害元素的分析就顯得十分重要。 xrf譜儀 以panalytical為例 wdxrf： magix、cubix、venus200 edxrf： minipal，minimatetaiheiyos ofunato 工廠用pw2606譜儀進(jìn)行常規(guī)分析，pw2404做痕量元素分析。大連日本小野

2、田用magix對(duì)常規(guī)和痕量元素同時(shí)進(jìn)行分析。 基礎(chǔ)知識(shí)可參考 1.x射線熒光光譜分析 吉昂 陶光儀 卓尚軍 羅立強(qiáng) 編箸，中國(guó)科學(xué)院研究教材叢書，科學(xué)出版社，2003年 2.能量色散x射線熒光光譜分析 曹利國(guó) 成都科技大學(xué)出版社，1998年 本文就分析對(duì)象、基體校正、能量色散和波長(zhǎng)色散譜儀在分析分析中應(yīng)用等方面作簡(jiǎn)單介紹。 分析對(duì)象主要成份有nao、mgo、al2o3、sio2、so3、cao、fe2o3，有時(shí)還要分析cl。水泥中待分析微量元素含量范圍及檢測(cè)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基體效應(yīng)1、元素間相互影響當(dāng)用足夠高的電壓如50kv激發(fā)樣品時(shí)，可以使樣品中存在的元素均可產(chǎn)生相應(yīng)的特征x射線，即x射線熒光。這些特征x射線可以是k系線，也可能是l系線。水泥中經(jīng)常要分析的元素的吸收限能量和特征x射線能量列于表1。 表1. 水泥中經(jīng)常要分析的元素的吸收限能量和特征x射線能量待分析元素fnamgalsiskcafek系吸收限(kev)0.6871.081.3031.5591.8372.4703.6064.0377.10

4、1k線能量(kev)0.6771.041.2541.4871.7402.3073.3113.6906.400 試樣中的元素均可吸收所發(fā)射的特征x射線，這種吸收有光電吸收和散射吸收兩種，當(dāng)待測(cè)元素的特征x射線的能量大于基體中某一元素的k系吸收限，就可激發(fā)該元素，使之產(chǎn)生二次x射線熒光.1、元素間相互影響 a、從表1看元素間存在吸收增強(qiáng)效應(yīng)，z+1元素均可激發(fā)z元素，現(xiàn)以xrf分析專用系列水泥生料(gsb 08-1110-1999)為對(duì)象用magix分析結(jié)果為例說明問題。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指數(shù)校正:標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)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分析結(jié)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標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)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分析結(jié)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標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)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結(jié)論 以粉末壓片法分析gsb 08-1110-1999標(biāo)樣的校正曲線表明：在該標(biāo)樣的濃度范圍內(nèi)，直接用實(shí)驗(yàn)校正法制定校正曲線時(shí)，其rms、k 和校正曲線值與標(biāo)樣值均滿足質(zhì)量控制要求。 結(jié)果表明：生料的元素間吸收增強(qiáng)效應(yīng)可以忽略。2、顆粒度效應(yīng)顆粒度效應(yīng) 從上圖可以看出，顆粒度效應(yīng)有兩方面： 顆粒大小，即粒徑; 顆粒均勻性。顆粒度影響 生料粉碎時(shí)間與

11、強(qiáng)度的關(guān)系粉碎時(shí)間(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 增加研磨時(shí)間，并不只是減少平均粒徑，而是可以更小的顆粒填

12、允兩個(gè)較大的顆粒間的空隙，密度增加，使樣品表面更平。 逃逸深度相對(duì)于顆粒大小是相當(dāng)小的情況，陰影效應(yīng)陰影效應(yīng)(shadow effect)是有意義的，反之如果逃逸深度是大的，則楔入楔入效應(yīng)效應(yīng)(wedge effect)是有意義的。3、礦物結(jié)構(gòu)效應(yīng) 生料是由石灰石、粘土、粉砂巖或砂巖、硫酸渣及煤灰等和鐵礦石等混合而成，所分析的元素與這幾種礦物的來源和礦物結(jié)構(gòu)效應(yīng)有關(guān)。石灰石是水泥配料中主要成分，約占總量的80%左右，我國(guó)目前水泥廠使用的石灰?guī)r，按地質(zhì)年代分從寒武系到三疊系；按石灰?guī)r成因區(qū)分，既有沉積巖，又有變質(zhì)巖；按化學(xué)成分cao的含量 55.2%到30.0%。礦物結(jié)構(gòu)效應(yīng) 礦物相結(jié)構(gòu)礦物相結(jié)

13、構(gòu)差異引起 2 位移和元素在不同相中質(zhì)量吸收系數(shù)的差異，使強(qiáng)度產(chǎn)生變化。以gsb 08-1110-1999標(biāo)樣和工廠實(shí)際參比樣為對(duì)象來說明該問題礦物效應(yīng)引起2 角度的變化al2o3-1al2o3-2al2o3-3al2o3-4不同礦物來源配制的生料中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不同礦物來源

17、配制的生料中cao分析經(jīng)驗(yàn)系數(shù)校正不同礦物來源配制的生料中cao分析經(jīng)驗(yàn)系數(shù)校正不同礦物來源配制的生料中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標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)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不同礦物來源配制的生料中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標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)率(kcps)基體(%)(%)(%)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 用國(guó)標(biāo)生料分析山東東源生料結(jié)果 樣品號(hào)sio2al2o3fe2o3caomgoy1化學(xué)值13.122.292.1243.142.13xrf13.212.911.7644.202.00+0.09+0.62-0.361.060.13y2化學(xué)值13.262.572.3543.081.93xrf13.973.251.9954

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

24、42.662.44+0.48+0.99-0.351.110.11y7化學(xué)值13.712.472.3042.342.34xrf13.933.231.9643.422.22+0.22+0.76-0.341.080.12y8化學(xué)值13.942.562.5042.232.17xrf14.043.462.1243.422.12+0.10+0.90-0.381.190.05結(jié)論：1、從上表可見，分析的生料與實(shí)際生產(chǎn)樣的組份相近，如sio2的含量范圍從13.12%14.30%，al2o3的含量范圍從2.29%3.65%，fe2o3的含量范圍從2.12%2.50%，cao的含量范圍從1.55%43.14%。但

25、sio2的分析絕對(duì)差的變化從-0.26%到0.48%；al2o3分析絕對(duì)差的變化從0.62%到0.93%；fe2o3分析絕對(duì)差的變化從-0.34%到-1.13%；cao分析絕對(duì)差的變化從0.57%到1.19%；mgo的含量范圍從.13%2.55%，分析絕對(duì)差的變化在允許誤差范圍內(nèi)。2、sio2、al2o3、fe2o3和cao的分析絕對(duì)差來看，若用其中任何一個(gè)樣的xrf測(cè)定值與化學(xué)分析值之間的絕對(duì)差去修正d值，除al2o3的誤差為0.30%外，其它元素均超差。結(jié)論 礦物礦物效應(yīng)效應(yīng)和和顆粒顆粒度度效應(yīng)效應(yīng)是生料分析結(jié)果誤差主要來源； 以改變截距使 曲線平移的方法校正礦物效應(yīng)和顆粒度效應(yīng)有時(shí)雖然可

26、行，但數(shù)據(jù)在很大程度上不可信。 粉末壓片法的問題很復(fù)雜，無論在理論上還是實(shí)踐上均不是簡(jiǎn)單的，在目前要予以解釋是很困難的。如何解決顆粒度和礦物效應(yīng)用熔融法，在時(shí)間上是能滿足要求的；但可獲得最準(zhǔn)確的結(jié)果；使用粉末壓片法，需在標(biāo)樣與試樣諸礦物相匹配的情況下，并有足夠的數(shù)量。用經(jīng)驗(yàn)系數(shù)法對(duì)所測(cè)元素進(jìn)行校正亦可獲得可用于生產(chǎn)質(zhì)量控制的結(jié)果。數(shù)學(xué)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系數(shù)數(shù)值鎖住來源alpha for al2o34.4187 解鎖的回歸alpha for cao-1.3694 解鎖的回歸beta for sio2-3.1259 解鎖的回歸標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)率(kcps)基體(%)(%)(%)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系數(shù)數(shù)值鎖住來源alpha for sio2-3.718 解鎖的回歸標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)率(kcps)基體(%)(%)(%)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系數(shù)數(shù)值鎖住來源alpha for fe2o3-3.357 解鎖的回歸beta for sio2-4.3768 解鎖的回歸標(biāo)樣c(計(jì)算)c(化學(xué))diff(c)毛計(jì)數(shù)率(kcps)凈計(jì)數(shù)率(kcps)基體(%)(%)(%)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熔融法要有材質(zhì)為5%au95%pt的鉑金坩堝及模具，高溫爐最高溫度不得低于12000c，

41、熔劑有無水四硼酸鋰、偏硼酸鋰及其混合物，如a12(66%li2b4o7+34%libo2)熔劑。 用a12熔劑與試樣比例建議使用表2中所推薦的方法。表4中所用熔融時(shí)間應(yīng)根據(jù)熔融設(shè)備確定，若熔融設(shè)備無攪拌功能，應(yīng)人工將熔融體搖動(dòng)三次以上，保證熔融體均勻，澆鑄前，模具加熱至紅，澆鑄后，冷卻溫度應(yīng)根據(jù)試樣選擇，保證玻璃片透明、無折晶。 熔劑98%li2b4o7+2%nai。0.700克樣+7.00克熔劑。7000c預(yù)熱5分鐘，加熱至11500c熔 融，共20m。自然冷卻。不同礦物的熔融法條件 表4熔融方法的制樣條件樣品名稱試樣與熔劑比氧化劑預(yù)氧化溫度熔融溫度水泥和白云巖1.8:91克nh4no500

42、度1分鐘1100度4分鐘黏土和高岑土1.8:8同上同上1100度5分鐘砂巖和土址1:8,1份li2co3 1100度6分鐘礦1.8:8,1份li2co32克nh4no3200度預(yù)熱3分鐘1100度7分鐘礦渣1.8:8,1份li2co31克nh4no3500度預(yù)熱2分鐘1100度5分鐘礦渣，含硫1.8克樣加10ml硝酸,8克熔劑,1克li2co3 200度預(yù)熱3分鐘，500度預(yù)熱2分鐘1100度5分鐘鋁土礦1.8:8,1份li2co31克nh4no3500度預(yù)熱2分鐘1100度3.5分鐘石膏1.8:8,1份li2co31克nh4no3500度預(yù)熱1分鐘1100度3.5分鐘生料1.8:8,1份li2co31克nh4no3500度預(yù)熱2分鐘1100度3.5分鐘熟料1:8,1份li2co31克nh4no3500度預(yù)熱1分鐘1100度4分鐘