確認本實驗室檢驗方法與結(jié)果精密度的計劃方案

1、用于過程控制中吸油值吸碘值的內(nèi)控指標(biāo)公司概況（略）、QC小組簡介活動課題用于過程控制中吸油值吸碘值的內(nèi)控指標(biāo)小組名稱：品質(zhì)部檢驗QC小組組長：馬文紅小組類型：改進型成立時間：2009年1月注冊號：序號組內(nèi)成員職稱及學(xué)歷組內(nèi)職務(wù)組內(nèi)分工1馬文紅工程師組長兼統(tǒng)計分析制訂措施2于春山部長計劃協(xié)調(diào)制訂措施3孫玲梅工程師測量負責(zé)人落實措施4肖潔工程師執(zhí)行負責(zé)人落實措施5蔣凱大專測試人落實措施6張冬雁本科分析人員落實措施7薛李贊本科分析人員落實措施8莊榮梅中專測試人落實措施9趙愛玲大專測試人落實措施10劉匡欣大專測試人落實措施11馮亞娟中專測試人落實措施12馬勝芝中專測試人落實措施13杜盈盈大專測試人落實

2、措施活動時間；2009年1月一5月活動次數(shù)：12次出勤率：100%二選擇課題選題理由為生產(chǎn)部門提供吸油值吸碘值數(shù)據(jù)的準(zhǔn)確性是本實驗室的責(zé)任，但任何測試方法都受地區(qū)、水質(zhì)、試劑、環(huán)境、操作人、儀器設(shè)備等操作系統(tǒng)的影響，炭黑生產(chǎn)方與使用方均受這些因素的影響，這樣會造成在炭黑產(chǎn)品等級的判定，有時合格變優(yōu)等或優(yōu)等變合格或不合格現(xiàn)象，內(nèi)部外部都產(chǎn)生不信任的矛盾。操作系統(tǒng)誤差是有規(guī)律的，受測試方法精密度影響，首先在炭黑生產(chǎn)廠內(nèi)通過精密度試驗測量本實驗室的這兩種試驗方法的精密度；而后再通過不斷的交流，收集用戶的信息，掌握用戶實驗室的水平，在炭黑的實際生產(chǎn)過程控制中消除或降低誤差，依此合理的制定吸油值吸碘值的

3、內(nèi)控指標(biāo)來指導(dǎo)生產(chǎn)是極為必要的?，F(xiàn)狀調(diào)查在炭黑生產(chǎn)過程控制時，各品種炭黑吸油值、吸碘值指標(biāo)控制范圍一般按國標(biāo)給定的區(qū)域如N115品種炭黑：吸油值優(yōu)級H3±5,合格級H3土7;吸碘值優(yōu)級160±6,合格級160±8生產(chǎn)控制，使用方大部分按國標(biāo)給定的優(yōu)級品范圍來接收，這樣就要求生產(chǎn)方在生產(chǎn)制造時要提高產(chǎn)品質(zhì)量控制成本，生產(chǎn)方也要相應(yīng)的縮小指標(biāo)控制范圍以達到客戶滿意。（三）制定對策在制定炭黑產(chǎn)品質(zhì)量內(nèi)控指標(biāo)控制范圍時，考慮兩方面的影響因素，一是消除生產(chǎn)方內(nèi)部吸油值吸碘值測試方法精密度造成的影響（重復(fù)性標(biāo)準(zhǔn)差）；二是降低生產(chǎn)方與使用方不同實驗室產(chǎn)生的誤差影響（再現(xiàn)性標(biāo)準(zhǔn)差

4、）。目標(biāo)值土波動范圍消除再現(xiàn)性標(biāo)準(zhǔn)差>消除重復(fù)性標(biāo)準(zhǔn)差三精密度試驗實施方案精密度試驗嚴(yán)格按照GB/T6379測量方法與結(jié)果的準(zhǔn)確度（正確度與精密度）執(zhí)行。試驗計劃進行吸油值、吸碘值精密度試驗，按照GB/T6379的要求成立了試驗小組，分配了各成員的職責(zé)。吸油值試驗依據(jù)：GB/T3780.2炭黑鄰苯二甲酸二丁酯吸收值的測定；吸碘值試驗依據(jù)：GB/T3780.1橡膠用炭黑吸碘值試驗方法。所有試驗設(shè)備的預(yù)檢應(yīng)按標(biāo)準(zhǔn)方法中的規(guī)定進行；測試人員包括中間分析人員與成品分析人員共13人，每個測試人員做為一個獨立的試驗室進行測定，也就分為13組。要求測度人員熟練掌握吸油值、吸碘值測試方法。測試樣品（水平

5、）為我公司生產(chǎn)的所有品種：N115N121N134N234N220N330N375N326b其中吸油值及吸碘值水平有高有低。所有以上炭黑品種分別進行吸油值、吸碘值測試各需測定4次。完成測試需二個月時間。樣品準(zhǔn)備在決定試驗所需的樣品數(shù)量時，應(yīng)考慮到在獲得某些測試結(jié)果時會出現(xiàn)偶然的損失或稱量誤差，從而需要準(zhǔn)備的樣品數(shù)量應(yīng)當(dāng)足以滿足測試之用，并且允許適當(dāng)?shù)膬?。由?zhí)行負責(zé)人專人采樣，并將每一種樣品充分混對均勻，通過850即試驗篩，進行均質(zhì)化處理，以減少測試誤差。分罐貯存，所有的受試樣本都應(yīng)該用標(biāo)簽表明測試名稱并對樣品進行編號，測試時負責(zé)分發(fā)樣品給每個測試人。（三）測試要求每一個水平的一次測試需要一星

6、期內(nèi)完成，測試時由測試負責(zé)人把樣品編號后分發(fā)給各測試人。為避免潛在的環(huán)境影響，不同測試人的同一水平同一組的所有測試均在同日完成，所需樣品須在溫度范圍為（125±5）C烘箱里干燥1小時，再放入干燥器內(nèi)冷卻備用。沒有必要要求所有13組的4次測試都嚴(yán)格在一個很短的時間內(nèi)進行，不同組的測試可以不在同日內(nèi)進行；所有8個品種的測試都將由同一測試人做出，同一水平中一組4次測試應(yīng)該在重復(fù)性條件下進行；此外，在給定水平上做出的4次的測量要自始至終使用同一設(shè)備；如果在測試過程中一個測試人因故不能完成全部測試，那么可以由另一個測試人繼續(xù)剩下的測試，只要這個人員變更不是發(fā)生在同一水平同一組的4次測試中，而是

7、發(fā)生在13組中的兩個不同組上，任何這樣的人員變更都要隨測試結(jié)果一起上報；每一次每個操作人員作完一次測試后，均由執(zhí)行負責(zé)人將結(jié)果及時匯總，登記到原數(shù)據(jù)表，以防瞞報、漏報、錯報四試驗及數(shù)據(jù)分析炭黑吸油值試驗原始數(shù)據(jù)原始數(shù)據(jù)列于表1中，以單位10-5mVkg表示表1原始數(shù)據(jù)：炭黑吸油值測試人水平N115N121N134N220N234N330N375N326117.7132.9127.1115.0121.3103.1111.073.1111.8132.4127.1113.1120.1101.8112.371.11113.0131.4126.7113.1120.0102.6110.071.7112.0

8、131.9127.1114.1122.1102.3110.171.9113.0131.0127.5115.5125.0103.0110.973.0111.5131.8128.0114.1122.0102.5111.872.02111.8131.5128.5114.2123.0102.6112.573.0124.0132.2127.0114.0120.2102.5111.672.2113.1131.0125.1113.5119.0101.3111.272.1113.8131.0127.6114.5121.4102.0111.072.03114.0131.2127.9115.0123.8102.8

9、112.072.8114.0131.1127.0114.5121.2101.9113.072.2111.2131.8127.5113.0123.0102.3111.074.0112.0131.0127.2113.5122.0101.5111.273.04113.0131.0127.0113.5122.0102.0111.072.5112.0131.0126.9112.2122.0103.0111.073.0109.2130.5124.0114.5121.599.8109.071.0113.0131.5127.5114.6123.4101.9111.572.55113.0131.5128.511

10、7.5123.0104.0113.872.2113.5132.0127.5114.5124.9103.0112.072.86109.1111.8112.0111.0130.1130.4130.3131.4124.3126.9126.2127.0112. 3113. 1114. 3112.2120.0122.1121.0122.0100.9101.2101.1101.0109. 1111.1110. 3111.070.972.071.472.0112.0132.0127.0114.5121.5101.0110.073.5112.0130.5127.0114.0122.3101.0110.273.

11、57112.0130.0126.0113.0120.2102.2112.072.0111.0131.0127.0114.0122.3101.3110.873.0113.0132.5128.0114.5121.3102.8111.172.2112.5132.0128.0114.0121.5102.0111.072.08112.0132.0128.0114.2122.0102.5111.272.5114.0132.8127.5114.2121.5102.0110.872.0111.2131.0127.8115.0122.0101.0111.571.0111.5131.5128.0115.2123.

12、0102.0111.572.09123.0131.0128.0115.5122.5102.0111.271.0111.5131.5128.0115.5122.0101.5112.072.0116.1129.1128.8115.0120.1104.4113.173.9113.8133.1129.0115.0122.0104.0113.973.010114.0133.5127.2115.5119.1104.5112.172.7113.8134.0130.2103.5123.0104.0114.072.8112.1131.0126.0112.5120.2100.2110.172.5112.5132.

13、0127.5113.1120.5103.0111.272.011111.0131.0126.2113.0120.2101.2110.072.5111.5132.1128.0114.0121.0102.0110.273.0112.5133.0130.0115.0122.0102.0111.073.1112.0131.0127.5114.0123.0102.0112.571.012112.0131.2128.0113.5121.0101.0111.071.0112.0131.5127.5113.0123.0102.0111.072.0112.0130.1127.0115.0121.0103.011

14、1.072.0112.0133.0126.0114.0121.0103.0111.172.113112.1130.8127.0113.0122.0101.8110.072.0111.1130.9127.0113.2121.0101.1110.572.1以上測試結(jié)果中測試人2號與9號、10號在N115N220測試中用錯樣品造成數(shù)據(jù)偏離，對這三個數(shù)據(jù)予以剔除，那么這三個試驗室在N115與N220的水平測試次數(shù)為n=3,其余測試人各水平測度次數(shù)均為n=4。單元平均值(y)單元平均值(y)按表1的格式列于表2中，以單位lO-Wkg表示表2吸油值單元平均值測試人水平NU5N121N134N220N234

15、N330N375N3261112.12132.15127.00113.82120.87102.45110.8571.952112.10131.62127.75114.45122.55102.65111.7072.553113.72131.07126.90114.37121.35102.00111.8072.284112.05131.20127.15113.05122.25102.20111.0573.125112.17131.37126.87115.27123.20102.17111.5772.126110.97130.55126.10112.72121.27101.05110.3771.58

16、7111.75130.87126.75113.87121.57101.37110.7573.008112.87132.32127.87114.22121.57102.32111.0272.189111.40131.25127.95115.30122.37101.62111.5571.5010114.42132.42128.80112.12121.05104.22113.2773.1011111.77131.52126.92113.15120.47101.60110.3772.5012112.12131.67128.25113.87122.25101.75111.3771.7813111.801

17、31.20126.75113.80121.25102.22110.6572.05單元平均值應(yīng)比原始數(shù)據(jù)的測試結(jié)果有效數(shù)字多一位.吸油值標(biāo)準(zhǔn)差（S）吸油值標(biāo)準(zhǔn)差（S）列于表3中，以單位10-51m/kg表示表3吸油值標(biāo)準(zhǔn)差測試人水平NU5N121N134N220N234N330N375N32610.5960.6450.2000.9141.0080.5451.0660.83920.7940.5060.6450.7052.0020.2380.6580.52630.4270.0961.2570.6291.9620.6160.9090.35940.7370.4000.2640.6140.5000.627

18、0.1000.62951.997*0.6291.974*1.484*1.3981.801*1.98*0.78961.3220.5801.2520.5560.9840.1290.9220.53270.5000.8540.5000.6290.9910.5680.9000.70780.8540.3950.2500.2060.2990.3950.1710.23690.1730.2890.1000.2450.4790.4790.3320.577101.1202.247*1.2330.2891.7710.2630.8810.548110.6600.6080.9780.6240.3771.1890.5560

19、.408120.2500.9071.1900.8540.9570.5000.7501.001130.1691.2520.5000.9090.5000.9390.5010.058一致性和離群值的檢查n=4,p=13,對表3標(biāo)準(zhǔn)差用柯克倫檢驗法，柯克倫檢驗5%缶界值為0.307；%臨界值為0.369（1）如果檢驗統(tǒng)計量小于或等于5%缶界值，則接受被檢驗項目為正確值；(2)如果檢驗統(tǒng)計量大于5%缶界值，但小于或等于1%臨界值，則稱被檢驗的項目為岐離值,且用單星號標(biāo)出（*）（3）如果檢驗統(tǒng)計量大于1%缶界值，則被檢驗項目稱為統(tǒng)計離群值。且用雙星號標(biāo)出（*）檢驗結(jié)果如表3所示，離群值被剔除，而岐離值仍然

20、參與后續(xù)計算。剔除的離群試驗人為5號在N115N330N375水平和10號測試人在N121水平的測試數(shù)據(jù)。將格拉布斯檢驗應(yīng)用于單元平均值表2,沒有單個的歧離值或離群值吸油值總平均值（m）、重復(fù)性（S）、再現(xiàn)性（0）的計算T-!njyi 5165測試人數(shù)P=12以水平1 : N115為例,2E n（y）諸方差計算如下579980.5ni 462?4ni178?5 g l)Si 19.321622hSr- 0.56828p29 J2T3 T1s2)iT3(P l)i2/0.821402SI T3(P 1)T32 T4c 22SR2 Sr2SLnu *112.28Sr0,7538SR1.1788注：

21、n一做樣次數(shù)；P測試人數(shù)；s一標(biāo)準(zhǔn)偏差；y單元平均值；s試驗室內(nèi)重復(fù)性標(biāo)準(zhǔn)差；m各水平總平均值；S實驗室間標(biāo)準(zhǔn)偏差;&試驗室再現(xiàn)性標(biāo)準(zhǔn)差以此類推，分別對18項水平進行計算，其結(jié)果列于下表4：表4炭黑吸油值精密度水平PMSrSrN11512112.280.7531.178N12112131.400.6640.764N13413127.310.9621.121N22013113.880.7501.100N23413121.691.1691.270N33012102.120.6100.968N37512111.230.7201.017X3261372.280.6160.879。炭黑吸碘值試驗

22、原始數(shù)據(jù)原始數(shù)據(jù)列于表5中，以單位g/kg表示表5原始數(shù)據(jù)：炭黑吸碘值測試人水平N115N121N134N220N234N330N375N326159.2120.8142.7122.2120.582.389.781.1157.7119.8140.7122.0120.582.589.081.21159.2120.5142.7122.3119.382.389.681.2157.0120.3142.5122.2121.182.389.780.2158.0120.8142.5122.2120.082.689.681.2159.7119.3144.5122.6120.082.590.181.22160.

23、5121.5145.0122.6120.282.589.681.6162.5113.7144.5123.7121.082.589.881.2160.0121.3145.0122.7121.182.690.182.1160.0121.2145.0122.6120.283.691.182.13158.7120.0142.5122.2119.682.389.881.2158.2120.2142.5121.5119.382.589.781.2160.0121.2144.7122.5120.783.691.282.1160.0121.0143.5122.5120.083.190.081.24157.51

24、20.0142.2122.5118.781.589.382.3158.7121.2142.2122.5120.583.090.081.2160.0122.5145.123.7121.583.791.082.5160.0121.2144.0123.0121.082.391.081.55159.0119.7142.5122.7120.082.591.081.2159.0119.0142.5122.5120.282.589.781.2160.5122.3146.5123.8121.183.390.682.5159.7121.1143.0122.7120.783.090.281.56157.7120.

25、1142.2122.3119.682.290.280.8159.0121.1142.5123.1120.082.689.681.2159.5121.0143.7122.2120.682.390.182.2160.0120.1142.5122.5120.083.090.081.77158.7119.2142.0121.2119.782.589.881.1159.5121.2142.5121.5120.682.589.881.0159.2121.2144.5123.1121.082.790.081.2161.2121.5144.5123.7121.083.791.182.28157.5119.71

26、42.7121.5119.382.389.381.0158.00120.1142.5121.8121.082.589.681.2160.0121.2145.0123.1120.282.690.181.0160.0121.2145.0123.1120.182.590.181.59159.7118.7144.5122.5120.082.590.081.2162.5121.2145.0123.5121.282.590.081.2160.0120.1142.7122.3119.782.590.081.210158.2120.1143.0121.3119.882.589.381.1157.5119.81

27、42.7121.3119.382.789.681.1159.7119.8143.7121.0119.382.389.881.0157.7120.3142.7121.6119.582.089.381.0157.7121.1142.7121.5119.582.689.881.111159.2120.8143.7122.2119.683.089.881.0159.5120.2145.0121.5119.381.889.381.0上表中2號測試人在N121的測試中用錯樣品造成有一個數(shù)據(jù)偏聽偏離，這一錯誤數(shù)據(jù)予以剔除，其做樣數(shù)相應(yīng)的n=3參與后續(xù)計算。單元平均值(y)單元平均值(y)按表1的格式列于表6

28、中，以單位g/kg表示表6吸碘值單元平均值測試人水平N115N121N134N220N234N330N375N3261158.31120.40142.18122.21120.3782.4089.5380.962160.18120.58144.12122.81120.3182.5389.8081.333159.25120.7143.75122.28120.0982.7790.2181.684159.06120.8143.18122.50120.0082.8190.1581.745159.50120.62143.62123.00120.6882.7890.6881.626159.25121.181

29、43.56123.27120.3782.8190.1881.537159.43120.40142.68121.87120.24782.5989.9681.538159.00120.65143.56122.56120.5982.8490.0281.439160.56120.62144.87123.06120.4082.5390.0681.2510158.87119.99143.06121.52119.5982.5389.7181.1211159.56120.65113.56121.71119.4982.3789.6281.03吸油值標(biāo)準(zhǔn)差(s)吸油值標(biāo)準(zhǔn)差(s)列于表7中，以單位g/kg表示表7

30、吸碘值標(biāo)準(zhǔn)差實驗人水平N115N121N134N220N234N330N375N32611.1250.4130.9650.1550.7290.0650.3580.48221.8631.0941.1080.6500.4730.0600.2390.18530.8890.6931.4430.5610.7800.5720.6220.50241.1960.5951.1960.0000.8890.9130.7880.58350.5771.5611.4360.5400.6880.6490.6250.59561.1720.9211.9830.6390.6840.4820.4150.69670.5150.909

31、0.7460.5950.4420.2780.1200.58181.6700.8511.0871.0530.8150.6250.7730.55491.2971.2500.2500.4140.5720.0600.0690.204101.1990.1440.4730.5880.2580.1590.2780.102110.9430.4111.0680.3590.1020.5310.2880.060一致性和離群值的檢查n=4,p=ll,柯克倫檢驗5%缶界值為0.348;1%缶界值為0.418。對表7進行檢驗無單個離群值和歧離值。將格拉布斯檢驗應(yīng)用于單元平均值表6,沒有單個的歧離值或離群值吸油值各水平總平

32、均值（隊重復(fù)性（工）、再現(xiàn)性（sR）的計算同吸油值數(shù)據(jù)處理方法一致，計算步驟略，結(jié)果列于表8：表8:吸碘值的精密度水平PIllSrSrN11511159.361.1961.204N12111120.610.9080.908N13411143.471.1611.230N22011122.430.5700.757N23411120.190.6290.663N3301182.630.4860.486N3751189.990.4800.499X3261181.380.1670.535五、內(nèi)控指標(biāo)與精密度測試方法的精密度應(yīng)是制定內(nèi)控指標(biāo)的重要依據(jù)。根據(jù)精密度計算各品種炭黑吸油值、吸碘值內(nèi)控指標(biāo)的方法如下：1 .計算項目的精密度（不確定值）。當(dāng)吸油值、吸碘值測試方法的再現(xiàn)性為相對偏差時，項目的目標(biāo)值/典型值或者極限值與再現(xiàn)性相乘即可；當(dāng)再現(xiàn)