譜儀水泥原材料分析中有效應(yīng)用

1、譜儀水泥原材料分析中有效應(yīng)用譜儀水泥原材料分析中有效應(yīng)用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。大連日本小野田用MagiX對常規(guī)和痕量元素同時(shí)進(jìn)行分析。譜儀水泥原材料分析中有效應(yīng)用 基礎(chǔ)知識可參考 1.X射線熒光光譜分析 吉昂 陶光儀 卓尚軍 羅立強(qiáng) 編箸，中國科學(xué)院研究教材叢書，科學(xué)出版社，2003年 X射線熒光光譜分析 曹利國 成都科技大學(xué)出版社，1998年 本文就分析對象、基體校正、能量

2、色散和波長色散譜儀在分析分析中應(yīng)用等方面作簡單介紹。 譜儀水泥原材料分析中有效應(yīng)用分析對象主要成份有NaO、MgO、Al2O3、SiO2、SO3、CaO、Fe2O3，有時(shí)還要分析Cl。譜儀水泥原材料分析中有效應(yīng)用水泥中待分析微量元素含量范圍及檢測限 (ppm)MagiXLLDV4.5Cr3.1Ni0.6Cu1.2Zn1.6As0.8Sr1.1Zr2.0Mo3.0Cd2.0Ba8.3Pb1.7Tl0.3最小值324510122202.022040100.6140301最大值240226802051200404201861103069050010譜儀水泥原材料分析中有效應(yīng)用基體效應(yīng)1、元素間相互影

3、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)0.6871.081.3031.5591.8372.4703.6064.0377.101K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

4、測元素的特征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.譜儀水泥原材料分析中有效應(yīng)用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)為對象用MagiX分析結(jié)果為例說明問題。譜儀水泥原材料分析中有效應(yīng)用Al2O3Philips AnalyticalCalibration details for Al2O3 in RM道: AlMatrix model:Classic模式:C=D+E.R.M比例道:背景:1Standards:10D:-0.52642E:0.1

5、2049F: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 -0.0440522.798621.7636S22.3832.380.0028425.287624.1446S42.8972.860.037429.7228.415S53.1453.110.0345731.843330.4663S63.3493.340.0093133.68232.1655S73.6323.590.0421836.124134.5131S83.8263.83 -0.0036137.846436.1249S

6、94.054.07 -0.0196239.725937.9839S104.3054.31 -0.0045141.984640.1011S114.4924.55 -0.0575443.530841.6528譜儀水泥原材料分析中有效應(yīng)用Al2O3 OF WSB譜儀水泥原材料分析中有效應(yīng)用SiO2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:1.92592E:0.11053F:0RMS:0.06675K:0.01808標(biāo)樣C

7、(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 113.1805112.829S814.84414.830.01425 117.2378 116.8768S

8、915.32215.35 -0.02846 121.5425121.195S1015.85815.89-0.0316 126.4337 126.0522S1116.33716.41 -0.07292130.746130.383譜儀水泥原材料分析中有效應(yīng)用CaO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:0.05609K:0.00869標(biāo)樣C(計(jì)算)C(化學(xué))Dif

9、f(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 -0.00844489.239479.86S443.

10、30543.290.0154 498.8127 489.2602S244.50144.50.00139516.92 506.9975S145.14545.10.04486526.716 516.5405譜儀水泥原材料分析中有效應(yīng)用結(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。譜儀水泥原材料分析中有效應(yīng)用2、顆粒度效應(yīng)譜儀水泥原材料分析中有效應(yīng)用顆粒度效應(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

11、粒均勻性。譜儀水泥原材料分析中有效應(yīng)用顆粒度影響 生料粉碎時(shí)間與強(qiáng)度的關(guān)系粉碎時(shí)間(s)MgAlSiKCaFe901.81753.385563.12611.176222.2593.3351801.82743.277764.361411.2186218.6593.4282401.83453.220564.391411.2133218.44553.43133001.83213.176464.582611.2285217.97393.4964300:901.00800.93821.0231.00470.98071.048240:1801.00390.98241.00051.00050.99901.0

12、096譜儀水泥原材料分析中有效應(yīng)用 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，則楔入效應(yīng)楔入效應(yīng)(wedge effect)是有意義的。譜儀水泥原材料分析中有效應(yīng)用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

13、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%。譜儀水泥原材料分析中有效應(yīng)用礦物結(jié)構(gòu)效應(yīng) 礦物相結(jié)構(gòu)礦物相結(jié)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)際參比樣為對象來說明該問題譜儀水泥原材料分析中有效應(yīng)用礦物效應(yīng)引起2 角度的變化譜儀水泥原材料分析中有效應(yīng)用Al2O3-1譜儀水泥原材料分析中有效應(yīng)用Al2O3-2譜儀水泥原材料分析中有效應(yīng)用Al2O3-3譜儀水泥原材料分析中有效應(yīng)用Al2O3-4譜儀水泥原材料分析中有效應(yīng)用不同礦物來源配制的生料中CaO分析Philips Anal

14、yticalCalibration 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 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#40.2

15、3240.27 -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#42.21541.550.66501489.06 479.607524.205S6#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 490.9

16、88524.223S5#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 -0.01667 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.

17、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譜儀水泥原材料分析中有效應(yīng)用不同礦物來源配制的生料中CaO分析經(jīng)驗(yàn)系數(shù)校正譜儀水泥原材料分析中有效應(yīng)用不同礦物來源配制的生料中CaO分析經(jīng)驗(yàn)系數(shù)校正譜儀水泥原材料分析中有效應(yīng)用不同礦物來源配制的生料中SiO2分析Philips AnalyticalCalibration details for

18、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 -0.3545522.798621.7636Y12.5362.290.2459129.912528.549S22.0492.38 -0.3312125.287624.1446Y52.8932.460.4326533.230631.7746Y72.8262.470

19、.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 -0.3389129.7228.415S52.7483.11 -0.3620431.843330.4663S62.9363.34 -0.4041233.68232.1655S73.1963.59 -0.3944836.12

20、4134.5131S83.3743.83 -0.4562137.846436.1249S93.5794.07 -0.4906139.725937.9839S103.8144.31 -0.4964541.984640.1011S113.9854.55 -0.5648443.530841.6528譜儀水泥原材料分析中有效應(yīng)用不同礦物來源配制的生料中Fe2O3分析Philips AnalyticalCalibration details for Fe2O3 in RM道: FeMatrix model:Classic模式:C=D+E.R.M比例道:背景:1Standards:18D:0.02636E

21、: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(%)(%)(%)S111.5831.370.2126233.418233.0562S101.8091.610.1991238.230837.8673S92.0381.860.1775643.06442.7195S82.32.10.1999448.640348.2928Y11.9562.12 -0.1643941.341840.9788Y72.1382.3 -0.1624545.23144.8435S72.5012.350.1507752.940552

22、.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 -0.2605447.605547.2205S62.7212.60.1211657.616357.2398S52.9622.840.1224562.76162.365S43.1753.090.0848167.266366.8758S

23、23.6333.580.0530477.01576.609S13.8623.820.0419581.8653譜儀水泥原材料分析中有效應(yīng)用 用國標(biāo)生料分析山東東源生料結(jié)果 樣品號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13.262.572.3543.081.93XRF13.973.251.99543.651.98+0.71+0.68-0.3550.570.05Y3化學(xué)值13.312.492.3943.101.82XRF13.053.221

24、.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14.302.652.4941.552.55XRF14.783.642.1442.662.44+0.48+0.99-0.351.110.11Y7化學(xué)值13.712.472.3042.342.34XRF13.933.231

25、.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%，F(xiàn)e2O3的含量范圍從2.12%2.50%，CaO的含量范圍從1.55%43.14%。但SiO2的分析絕對差的變化從-0.26%到0.48%；Al2O3分析絕對差的變化從0.62%到0.93%；Fe2O3分析絕對差的變化從-0.34

26、%到-1.13%；CaO分析絕對差的變化從0.57%到1.19%；MgO的含量范圍從.13%2.55%，分析絕對差的變化在允許誤差范圍內(nèi)。2、SiO2、Al2O3、Fe2O3和CaO的分析絕對差來看，若用其中任何一個(gè)樣的XRF測定值與化學(xué)分析值之間的絕對差去修正D值，除Al2O3的誤差為0.30%外，其它元素均超差。譜儀水泥原材料分析中有效應(yīng)用結(jié)論 礦物效應(yīng)和顆粒度效應(yīng)礦物效應(yīng)和顆粒度效應(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)踐上均不是簡單的，在目前要予以解釋是很困難

27、的。譜儀水泥原材料分析中有效應(yīng)用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)法對所測元素進(jìn)行校正亦可獲得可用于生產(chǎn)質(zhì)量控制的結(jié)果。譜儀水泥原材料分析中有效應(yīng)用數(shù)學(xué)校正方法的校正Philips AnalyticalCalibration details for SiO2 in RMChannel: SiMatrix model:ClassicModel:C=D+E.R.MRatio channel:Backgrounds:1Standards:19D:9.613E:0.36345RM

28、S: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)(kcps)S111.72111.130.5909382.80482.

29、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 103.23830.09964Y213.34513.260.08504109.39 109.06850.09415Y313.11413.31 -0.19612 101.0253 100.73

30、330.09562Y413.40913.5 -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 113.1805112.8290.11423Y614.54814.30.24767 11

31、6.7453 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 126.05220.13639S1116.42216.410.0118130.746130.3830.14368譜儀水泥原材料分析中有效應(yīng)用的校正Philips AnalyticalCalibration details for Al2O3 in RM道: AlMatrix model:Classic模式:

32、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 -0.0307829.912528.5490.10949S22.4022.380.0218325

33、.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 -0.0154134.628933.09540.10995Y22.6072.570.0368732.879331.38280.11951Y42.6432.570.0730834.972733.43720.11412Y62.6882.650.0381536.144534.5930.11265S42

34、.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 -0.0318437.846436.12490.16309S94.0564.07-0.013739.725937.98390.16732S104.3394.310.0290241.984640.10110.17116S114.5884.550.0380143.5

35、30841.65280.17553譜儀水泥原材料分析中有效應(yīng)用的校正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(%)(%)(%)S1139.16939.060.1088 435.1688 42

36、6.85230.38988S1039.6939.660.03006 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 470.67450.48803Y842.2942.230.0603

37、 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 504.69550.50513Y143.221

38、43.140.08093 512.3468 502.56830.5122S443.2543.29 -0.04049 498.8127 489.26020.52744S244.55644.50.05591516.92 506.99750.56685S145.24245.10.14152526.716 516.54050.58619譜儀水泥原材料分析中有效應(yīng)用的校正#Philips AnalyticalCalibration details for Fe2O3 in RM道: FeMatrix model:Classic模式:C=D+E.R.M比例道:背景:1Standards:18D:0.732

39、09E: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(%)(%)(%)S111.5431.370.1726333.418233.05620.24548S101.7211.610.1111838.230837.86730.2615S91.9181.860.0582843.06442.71950.27799S82.1492.10.0491848.640348.29280.29377Y12

40、.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 -0.2282148.436248.04620.32083Y52.3152.51 -0.1954947.605547.22050.3355S62.5922.6-0.00857.616357.23980.32