确认本实验室检验方法与结果精密度的计划方案

1、用于过程控制中吸油值吸碘值的内控指标公司概况（略）、QC小组简介活动课题用于过程控制中吸油值吸碘值的内控指标小组名称：品质部检验QC小组组长：马文红小组类型：改进型成立时间：2009年1月注册号：序号组内成员职称及学历组内职务组内分工1马文红工程师组长兼统计分析制订措施2于春山部长计划协调制订措施3孙玲梅工程师测量负责人落实措施4肖洁工程师执行负责人落实措施5蒋凯大专测试人落实措施6张冬雁本科分析人员落实措施7薛李赞本科分析人员落实措施8庄荣梅中专测试人落实措施9赵爱玲大专测试人落实措施10刘匡欣大专测试人落实措施11冯亚娟中专测试人落实措施12马胜芝中专测试人落实措施13杜盈盈大专测试人落实

2、措施活动时间；2009年1月一5月活动次数：12次出勤率：100%二选择课题选题理由为生产部门提供吸油值吸碘值数据的准确性是本实验室的责任，但任何测试方法都受地区、水质、试剂、环境、操作人、仪器设备等操作系统的影响，炭黑生产方与使用方均受这些因素的影响，这样会造成在炭黑产品等级的判定，有时合格变优等或优等变合格或不合格现象，内部外部都产生不信任的矛盾。操作系统误差是有规律的，受测试方法精密度影响，首先在炭黑生产厂内通过精密度试验测量本实验室的这两种试验方法的精密度；而后再通过不断的交流，收集用户的信息，掌握用户实验室的水平，在炭黑的实际生产过程控制中消除或降低误差，依此合理的制定吸油值吸碘值的

3、内控指标来指导生产是极为必要的。现状调查在炭黑生产过程控制时，各品种炭黑吸油值、吸碘值指标控制范围一般按国标给定的区域如N115品种炭黑：吸油值优级H3±5,合格级H3土7;吸碘值优级160±6,合格级160±8生产控制，使用方大部分按国标给定的优级品范围来接收，这样就要求生产方在生产制造时要提高产品质量控制成本，生产方也要相应的缩小指标控制范围以达到客户满意。（三）制定对策在制定炭黑产品质量内控指标控制范围时，考虑两方面的影响因素，一是消除生产方内部吸油值吸碘值测试方法精密度造成的影响（重复性标准差）；二是降低生产方与使用方不同实验室产生的误差影响（再现性标准差

4、）。目标值土波动范围消除再现性标准差>消除重复性标准差三精密度试验实施方案精密度试验严格按照GB/T6379测量方法与结果的准确度（正确度与精密度）执行。试验计划进行吸油值、吸碘值精密度试验，按照GB/T6379的要求成立了试验小组，分配了各成员的职责。吸油值试验依据：GB/T3780.2炭黑邻苯二甲酸二丁酯吸收值的测定；吸碘值试验依据：GB/T3780.1橡胶用炭黑吸碘值试验方法。所有试验设备的预检应按标准方法中的规定进行；测试人员包括中间分析人员与成品分析人员共13人，每个测试人员做为一个独立的试验室进行测定，也就分为13组。要求测度人员熟练掌握吸油值、吸碘值测试方法。测试样品（水平

5、）为我公司生产的所有品种：N115N121N134N234N220N330N375N326b其中吸油值及吸碘值水平有高有低。所有以上炭黑品种分别进行吸油值、吸碘值测试各需测定4次。完成测试需二个月时间。样品准备在决定试验所需的样品数量时，应考虑到在获得某些测试结果时会出现偶然的损失或称量误差，从而需要准备的样品数量应当足以满足测试之用，并且允许适当的储备。由执行负责人专人采样，并将每一种样品充分混对均匀，通过850即试验筛，进行均质化处理，以减少测试误差。分罐贮存，所有的受试样本都应该用标签表明测试名称并对样品进行编号，测试时负责分发样品给每个测试人。（三）测试要求每一个水平的一次测试需要一星

6、期内完成，测试时由测试负责人把样品编号后分发给各测试人。为避免潜在的环境影响，不同测试人的同一水平同一组的所有测试均在同日完成，所需样品须在温度范围为（125±5）C烘箱里干燥1小时，再放入干燥器内冷却备用。没有必要要求所有13组的4次测试都严格在一个很短的时间内进行，不同组的测试可以不在同日内进行；所有8个品种的测试都将由同一测试人做出，同一水平中一组4次测试应该在重复性条件下进行；此外，在给定水平上做出的4次的测量要自始至终使用同一设备；如果在测试过程中一个测试人因故不能完成全部测试，那么可以由另一个测试人继续剩下的测试，只要这个人员变更不是发生在同一水平同一组的4次测试中，而是

7、发生在13组中的两个不同组上，任何这样的人员变更都要随测试结果一起上报；每一次每个操作人员作完一次测试后，均由执行负责人将结果及时汇总，登记到原数据表，以防瞒报、漏报、错报四试验及数据分析炭黑吸油值试验原始数据原始数据列于表1中，以单位10-5mVkg表示表1原始数据：炭黑吸油值测试人水平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以上测试结果中测试人2号与9号、10号在N115N220测试中用错样品造成数据偏离，对这三个数据予以剔除，那么这三个试验室在N115与N220的水平测试次数为n=3,其余测试人各水平测度次数均为n=4。单元平均值(y)单元平均值(y)按表1的格式列于表2中，以单位lO-Wkg表示表2吸油值单元平均值测试人水平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单元平均值应比原始数据的测试结果有效数字多一位.吸油值标准差（S）吸油值标准差（S）列于表3中，以单位10-51m/kg表示表3吸油值标准差测试人水平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离群值的检查n=4,p=13,对表3标准差用柯克伦检验法，柯克伦检验5%缶界值为0.307；%临界值为0.369（1）如果检验统计量小于或等于5%缶界值，则接受被检验项目为正确值；(2)如果检验统计量大于5%缶界值，但小于或等于1%临界值，则称被检验的项目为岐离值,且用单星号标出（*）（3）如果检验统计量大于1%缶界值，则被检验项目称为统计离群值。且用双星号标出（*）检验结果如表3所示，离群值被剔除，而岐离值仍然

20、参与后续计算。剔除的离群试验人为5号在N115N330N375水平和10号测试人在N121水平的测试数据。将格拉布斯检验应用于单元平均值表2,没有单个的歧离值或离群值吸油值总平均值（m）、重复性（S）、再现性（0）的计算T-!njyi 5165测试人数P=12以水平1 : N115为例,2E n（y）诸方差计算如下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一做样次数；P测试人数；s一标准偏差；y单元平均值；s试验室内重复性标准差；m各水平总平均值；S实验室间标准偏差;&试验室再现性标准差以此类推，分别对18项水平进行计算，其结果列于下表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。炭黑吸碘值试验

22、原始数据原始数据列于表5中，以单位g/kg表示表5原始数据：炭黑吸碘值测试人水平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号测试人在N121的测试中用错样品造成有一个数据偏听偏离，这一错误数据予以剔除，其做样数相应的n=3参与后续计算。单元平均值(y)单元平均值(y)按表1的格式列于表6

28、中，以单位g/kg表示表6吸碘值单元平均值测试人水平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吸油值标准差(s)吸油值标准差(s)列于表7中，以单位g/kg表示表7

30、吸碘值标准差实验人水平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离群值的检查n=4,p=ll,柯克伦检验5%缶界值为0.348;1%缶界值为0.418。对表7进行检验无单个离群值和歧离值。将格拉布斯检验应用于单元平均值表6,没有单个的歧离值或离群值吸油值各水平总平

32、均值（队重复性（工）、再现性（sR）的计算同吸油值数据处理方法一致，计算步骤略，结果列于表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、内控指标与精密度测试方法的精密度应是制定内控指标的重要依据。根据精密度计算各品种炭黑吸油值、吸碘值内控指标的方法如下：1 .计算项目的精密度（不确定值）。当吸油值、吸碘值测试方法的再现性为相对偏差时，项目的目标值/典型值或者极限值与再现性相乘即可；当再现