标准解读
GB/T 37969-2019《近红外光谱定性分析通则》是中国国家标准之一,主要针对使用近红外光谱技术进行物质定性分析时的方法、步骤以及相关要求进行了规定。该标准适用于需要通过近红外光谱技术来识别或验证样品身份的场合,涵盖了从样品准备到数据分析全过程的操作指南。
在样品处理方面,标准强调了正确选择和制备样品的重要性,指出应根据待测物性质及分析目的采取合适的样品前处理方法,以确保获得可靠的结果。同时,对于不同类型的样品(如固体、液体等),给出了相应的推荐处理方式。
关于仪器设备的选择与校准,标准提出了具体的要求。它建议使用符合特定性能指标的近红外光谱仪,并且定期对仪器进行维护与校正,保证其处于良好的工作状态。此外,还介绍了如何建立有效的参考数据库,这对于提高定性分析准确性至关重要。
数据采集过程中,标准详细描述了实验条件设定、背景扣除、信号平滑等关键步骤,并强调了重复性和再现性的重要性。为了确保结果的一致性和可比性,提出了多次测量平均值作为最终结果的原则。
如需获取更多详尽信息,请直接参考下方经官方授权发布的权威标准文档。
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文档简介
犐犆犛71.040.99
犖30
中华人民共和国国家标准
犌犅/犜37969—2019
近红外光谱定性分析通则
犛狋犪狀犱犪狉犱犵狌犻犱犲犾犻狀犲狊犳狅狉狀犲犪狉犻狀犳狉犪狉犲犱狇狌犪犾犻狋犪狋犻狏犲犪狀犪犾狔狊犻狊
20190830发布20200301实施
国家市场监督管理总局
中国国家标准化管理委员会
发布
??
??Ⅰ…………………………
1??
1………………………
2???????
1…………………………
3?????
1………………
4?????
2………………
5???????
3…………………………
6????
3…………………
7????
3…………………
8??
3………………………
9?????????????
4…………
10???????
5…………………………
11????????
6………………………
12??????
6……………
13?????????
6……………………
14??????
7……………
15??????
7……………
16????
7…………………
17????????
8………………………
18???????、
???????8……………………
19????????????
8……………
??A(?????)???????????????9……………
??B(?????)犉??????18…………………
??C(?????)???????、???????20……………
??D(?????)???????PLSDA?????????????21……
??E(?????)????????????????SIMCA???24………
犌犅/犜37969—2019
??
?????GB/T1.1—2009???????。
??????????????????。
????????????????????(SAC/TC481)??。
???????:???????????、??????、????、?????????、??
?????????、???????????、?????????????、????????、?
?????、?????????、????(??)??????、????????????、???
???????????、???(??)??????。
??????:???、???、???、??、???、???、???、???、???、???、
??、???、???、??、???、???、???、???、??、???、???、???、??、
???、???、???、??、???。
Ⅰ
犌犅/犜37969—2019
???????????
1??
???????????????????????、????、????、????、??、??
??????、??????、????????????。
???????????12820cm-1~4000cm-1(?780nm~2500nm)???????
??。
2???????
??????????????????。??????????,????????????
?。???????????,?????(????????)??????。
GB/T8322?????????
GB/T29858—2013??????????????
3?????
GB/T8322??????????????????。
3.1
????狋狉犪犻狀犻狀犵狊犪犿狆犾犲狊
????learningsamples
????referencesamples
??、??????????。
3.2
???狋狉犪犻狀犻狀犵狊犲狋
???learningset
???referenceset
???????。
3.3
????狏犪犾犻犱犪狋犻狅狀狊犪犿狆犾犲狊
??????????????,???、???????。
3.4
???狏犪犾犻犱犪狋犻狅狀狊犲狋
???????。
3.5
??狋狉犪犻狀犻狀犵
??learning
?????????、????????????,?????????。
1
犌犅/犜37969—2019
3.6
?犮犾犪狊狊
???、??????????????。
3.7
???狉犲犮狅犵狀犻狋犻狅狀狉犪狋犲
??????????????????????????????,???????????
?????????。
3.8
?????犱犻狊犮狉犻犿犻狀犪狀狋狉犪狋犲
??????????????????????????????,???????????
?????????。
3.9
??????狆犪狋狋犲狉狀狉犲犮狅犵狀犻狋犻狅狀犿犲狋犺狅犱
?????(????)?????。
3.10
??????????狊狌狆犲狉狏犻狊犲犱狆犪狋狋犲狉狀狉犲犮狅犵狀犻狋犻狅狀犿犲狋犺狅犱
??????????????????。
3.11
??????????狌狀狊狌狆犲狉狏犻狊犲犱狆犪狋狋犲狉狀狉犲犮狅犵狀犻狋犻狅狀犿犲狋犺狅犱
?????????????????。
3.12
??????狇狌犪犾犻狋狔犮狅狀狋狉狅犾狊犪犿狆犾犲
????????????????,???????????,??????????????
???????。
4?????
4.1????
???????????????????????,??????????????,????
???、??????????????、??,?????????????,??????????
???,?????????????????????(????),??????????????
?????,???????????????。
4.2??????
4.2.1??????????????????????????????。
4.2.2????????????????????,
?SIMCA(softindependentmodelingofclass
analog)、?????????(partialleastsquaresdiscriminantanalysis
,PLSDA)、??????
(artificialneuralnetworks,ANN)??????(supportvectormachine,SVM)?。???????
????????????????????,???????????????,????????
?????????????????,??????。SIMCA??????????(PLSDA)?
2
犌犅/犜37969—2019
??????,????A。
4.2.3?????????????????(principalcomponentanalysis,PCA
)???????
(??????)???(hierarchicalclusteranalysis,HCA)?。????????????????
?,????????????????。????????????????????。
5???????
????????????????????,?????????????????:
a)??????????????、??、?????????;
b)?????(meancentering)、???(autoscaling)、MSC(multiplicativescattercorrection)、
SNV(standardnormalvariate)、???????????????????、????
??;
c)SIMCA?PLSDA???????????、??????;
d)????????????;
e)??????????????????、??????;
f)???????、?????。
6????
?????????GB/T29858—2013??5??????????。
7????
??????GB/T29858—2013??6????????????。
8??
8.1??
????????????????????????、?????。
8.2???????
8.2.1???????,
????????????、?????,???????????????
?????????????。
8.2.2?SIMCA?PLSDA????????,
????犃?(>3)????????,?????
??,??????????????6犃???;?????????????????,????
???,??????????????6(犃+1)???;?????????????????,?
???????24?????。
8.2.3???PCA????????????,
????????,??????????????
??????,????????????????,????????,???????,?????
????????10犃?。
3
犌犅/犜37969—2019
8.3???????
8.3.1??????????、
???????,??????????????????????
??,?????????????????????。
8.3.2???????????????????,
????????????犃≤5,??????
??????20;????????????犃≥5,??????????????4犃。
8.3.3??????????????。????????????????????????,
?
???????????????。
9?????????????
9.1?????????????????:
a)???????????????????????????????;
b)??????????,??????????????????????????,??
????????;
c)????????????????,???????????,????????????
??????????,???????????,??????????????????
?,???????,??????????????,?????????;
d)?????????????????????????????,??????????
????。
9.2?????????????????????,
???????1。
4
犌犅/犜37969—2019
?1??????????????
10???????
10.1????????,
??????????????????(???、????)??????
???????,?????????????????,???????。
10.2????????,
????:??、??、MSC?SNV?。???????????????
?,?????????????;????????,????????;MSC?SNV??????
5
犌犅/犜37969—2019
????????。???????????????,???????????????????
????,???????????????????????,????????????????
?,?????????。
10.3????????、
??????????????,??????????????????
??。
11????????
11.1?????????????????????????,
??????、??????,??
???????????(????????/??)??。
11.2???????????,
?????????????????????????????
???、Fisher????,??????????,????????????????????,??
?????????。?????????????????,??????????,??????
??????????????。???????????????????。
11.3?????????????????????????,
???????????????
?,?????????????????。
12??????
12.1??????????
????????????,??????,??????????????????????,
????A;??犉??,??????,?????B??犉??????,??????????。
???????????????????????????。
12.2???????
SIMCA?PLSDA???????????,??????????????,???????
???????,????A。
12.3??????
12.3.1???????????????????,
????????????????????
????????,?????。
12.3.2??????,
??????????????,???????????????????
????,????????????,????A。
12.3.3????????????????????,
????????;???????????
???????????,?????????,??????????????????,????
?????????,???????,?????????。
13?????????
13.1?8.3????????????????,
??????????????,???????
?????,??????????????????。
13.2??????????,
?????????????????;??????????,??
?????????????????。??,??????????????。?????,???
6
犌犅/犜37969—2019
??????????。???????,?????????????,????????????
??。??????????,????????????,?????????????,????
???????,?????????????,???????????。
13.3???????(confusionmatrix)
????????????????????,?????
??????????。
13.4????????????,
?16.1。
14??????
14.1???????????,
??????,????????????,??????????
?????????????????。
14.2????????????????????,
??犉?????????????,???
????犉?????,????B。
14.3????????,
?16.2。
15??????
15.1??????????,
????????????????????????。?????
??????,????????????,???????????,?????????????
????,??????????????。
15.2??????????????????????????????。???????,
??
??????????????,?????????????,??????????。?????
???,????????、????,????????,??????????,????????
?????????????。???????????????,??????????????
??,?????????????????。
?:????????????????????,??GB/T29858—2013????????????。
15.3?????????????,
???????????????????????????
??????。
15.4?????????,
?16.3。
16????
16.1??????????
??????????????????:
a)????????????;
b)?????????,????????、??、?????;
c)??????,??????????????、??、????、??、?????;
d)????,????、???;
e)????、??、??????????????????;
f)?????,??????????、????????????????、???????
?、??????????、?????????、?????????????;
g)??????????,???????????、????、?????;
7
犌犅/犜37969—2019
h)??????????,?????????????????????????????;
i)???????????。
16.2??????????
??????????????????:
a)??????、??、??、????;
b)????、????;
c)?????:????、??、?????;
d)????,????、???;
e)????、??、??????????????????;
f)??????;
g)??????????,?????????????????????????????;
h)???????????。
16.3???????
???????????????:
a)????????,??????????????????????;
b)???????????????,????????、???????;
c)???????????????(???????)??????????;
d)???????????????(???????)??????????;
e)??????????(???????)????、?????(??)?????;
f)????????????????????????????????。
17????????
???????????????????????:
a)????????????????,????????????;
b)???????????????????????、?????????????;
c)????????????????????????,?????????????;
d)??????????????????,???????????????;
e)????????,??????????,?????????。
18???????、
???????
???????????,???????、???????,????C。
19????????????
19.1???????PLSDA?????????????,
????D。
19.2????????????????SIMCA
???,????E。
8
犌犅/犜37969—2019
??犃
(?????)
???????????????
犃.1犛犐犕犆犃????
犃.1.1犛犐犕犆犃????????
SIMCA??????????????????????????,?????????,??
????????PCA???,???????????????????。
犃.1.2???????????????
??????????????????。?????,??????狀????(?????)
???????狓犻??????,??(A.1):
狓犻=[狓犻1狓犻2…狓犻狀]…………(A.1)
??,?犿?????????,?????犿×狀????????,??(A.2):
犡犿×狀=
狓11狓12…狓1狀
狓21狓22…狓2狀
…
狓犿1狓犿2…狓犿狀
熿
燀
燄
燅
…………(A.2)
?犡犿×狀???????,???????????????????犡犿×狀?????????
????????????????????犉1,犉2,…,犉犃(犪=1,2,3,…,犃,?犃<狀),?????
?,?犉1??????,犉2??????,????。?犃?????????????????,?
????????,????????????犡犿×狀????。??,???????犡犿×狀????
?????????????????,????,???犡犿×狀????????。???????
???,????Var(犉犪)????犪????犉犪??????,????犃?????,?犃??
???????????????λ犪(?????,eigenvalues)??,???(A.3)????:
∑
犃
犪=1Var
(犉犪)=∑
犃
犪=1λ
犪
…………(A.3)
??:
Var(犉1)≥Var(犉2)≥…≥Var(犉犪)
<0
,λ1≥λ2≥…≥λ犪
<0
。
??????犉1????????,?????犉2??,????。??????Var(犉犪)?
?、???λ犪???,???犉犪??????????。????????,?犪????犉犪???
?????????????。??,?犃????????????[∑
犃
犪=1Var
(犉犪)]??????
?(∑
狀
犼=1犙
2
犼)
???,????????????(cumulativepercentvariance,CPV,???????)
???犃????犉1,犉2,……,犉犃?????????????????,CPV犃??(A.4)??
??:
CPV犃=∑
犃
犪=1Var
(犉犪)
∑
狀
犼=1犙
2
犼
=
∑
犃
犪=1λ
犪
∑
狀
犼=1犙
2
犼
…………(A.4)
9
犌犅/犜37969—2019
??犃?????????????????(?85%),??,犃????犉1,犉2,…,犉犃???
??85%???????????????????,??,???????CPV????????
??????????。
???????,???????(??狇?)????????:
犡狇=犡狇+犜狇犘犜
狇+犈狇
…………(A.5)
??:
犡狇———?狇???????????????,??????,???犡狇???????;
犜狇———?狇???????;
犘狇———?狇??????;
犈狇———?狇??????。
?????狇?????犡狇????????狓狇
犻犼
????????狓^狇
犻犼
,??,狓狇
犻犼
??????
????(A.6)??:
狓狇
犻犼
=狓狇犼+狓^
狇
犻犼
+犲
狇
犻犼
=狓狇犼+∑
犃狇
犪=1
狋
狇
犻犪狆
狇
犪犼
+犲
狇
犻犼
……(A.6)
??:
狓狇
犼———?狇???犼???;
狓^狇
犻犼
———???????狓狇
犻犼
?????,??∑
犃狇
犪=1
狋
狇
犻犪狆
狇
犪犼
;
犃狇———?狇?????????;
狋
狇
犻犪———?狇????犻??犪?????????;
狆狇
犪犼
———?狇????犼??犪?????????;
犲
狇
犻犼
———?狇????犻???犼????,??(狓
犻犼
-狓^
犻犼
)。
???????,??????????????,?????????????,??????
?,???????????????????????????;???????????????
???????????,?????????????。??????????????????
????、???????????,??????。??????,??????????????,
??????????,????,??????????。??,????????????,???
?????????,????????,??????,????????????????,???
?SIMCA?????????。
犃.1.3???????
?????????犃???????????????。???????????????
?????。??,??????????,??????????,?????,?????????
??。??????????,?????????????,?????,????????,???
??????????????????????。???????????????????,?
??????(crossvalidation)??????????????????。????????,??
?????????(?????????)?,???????????????????????。
?????????????,????????????????,??????????????
?????????。??,??????????????????PRESS(predictiveresidual
errorsumofsquares)??(A.7)????:
PRESS=∑
犿
犻=1∑
狀
犼=1
犲
2
犻犼
=∑
犿
犻=1∑
狀
犼=1(
狓
犻犼
-狓^
犻犼
)
2
……(A.7)
?????????????,??????????????,???????????,??
01
犌犅/犜37969—2019
?????????????????????????。??????????????,???
?????????,???????????????,??PRESS?。??????????,
??????,??????????????PRESS?,????????????。?PRESS
?????????????????,???犉?????PRESS犃?PRESS(犃+1)???????
??,???犉???????(A.8)??:
犉=
狀
狀-犃-1
PRESS犃-PRESS(犃+1)
PRESS(犃+1)
()…………(A.8)
犉??????????5%,???犉0.05[狀,(狀-犃-1)]????[狀,(狀-犃-1)]?,?犉?
????????。??犉??????,??PRESS犃?PRESS(犃+1)????????,????
?????????????????。??,?????????犃。????????????
?,?????????????????????。
????????????,???PRESS????,????????。??,??????
??,??????????。
??????,????????????????????????????????,??,
?????????????????????????。
????????????CV2???????????,??????犡??????狓犽,?
??????CV2??????????CV2
cum????(A.9)
??(A.10)????:
CV2=1.0-
PRESS犃
PRESS(犃-1)
()
犽
…………(A.9)
CV
2
cum=1.0-∏
PRESS犃
PRESS(犃-1)
()
犽犪
[][犪=1,…,犃]……………(A.10)
??
PRESS犃
PRESS(犃-1)????1.0,
???,CV2????,??????????。????????
????,PRESS?????,??????????,??,???????????????,??
??????,???????????????????????。
犃.1.4??????????
??????????????????????????????????,???????
???????,????????????????????????,???????????。
???????,??Hotelling’s犜2??、犉??????????????????????。
Hotelling’s犜2,??犜2,
?????????,?????????????。???犿???
?????????,???????犃,?????????犻???????????,?犜2??
(A.11)????:
犜2犻=∑
犃
犪=1狋
2
犻犪
狊
2
狋犪
…………(A.11)
??:
狋犻犪———?犻???????犪????????。
狊
2
狋犪———?犻???????犪????????狋???。
??Hotelling’s犜2??,??????犻????????????????????,???
???,??犜2,??犉?????,犉??(A.12)????:
犉=犿(
犿-犃)
犃(犿2-1)
犜2犻…………(A.12)
??????,犉?????????5%(?1%),???犉α(犃,犿-犃)????(犃,犿-犃)
11
犌犅/犜37969—2019
?,?犉?????????。??
犜2犻>犃(
犿2-1)
犿(犿-犃)
犉α(犃,犿-犃)(α=5%,?1%)…(A.13)
??犻??????95%(?99%)???????,????????,?????????。
???????????犻????????,??犙2
犻,
?犙2
犻??(A.14)
????:
犙2犻=∑
狀
犼=1
犲
2
犻犼
狀-犃狇
…………(A.14)
??:
犲
狇
犻犼
———?狇???犻???犼????。
犃狇———?狇??????。
??,??犿??????????狇?,????????,??犙2,?犙2??(A.15)??
??:
犙2=∑
犿
犻=1∑
狀
犼=1
犲
2
犻犼
(犿-犃狇-1)(狀-犃狇)…………(A.15)
????????????狇????????????????,?????????,???
????????,??????????????????????。
??,???犉??????犻?????犙2
犻??????????犙2??????????
??????。???(A.14)??(A.15)??(A.16):
犉=犙
2
犻
犙2
…………(A.16)
??????,犉??????????5%(?1%)。???犉犪[(狀-犃),(犿-犃-1)(狀-犃)]
????[(狀-犃),(犿-犃-1)(狀-犃)]?,?犉?????????。??
犙2犻>犙2犉α[(狀-犃),(犿-犃-1)(狀-犃)][α=5%(?1%)]…………(A.17)
??犻??????95%(?99%)???????,???犻?????,??犻?????,?
????????。
?????,??????????????,?????????????????????
?,???犉???,??????????。???????,??????????????,?
????????????????????,??????、?????????????????
?,????犜2犙2??????????,???????????。????????????
?????????,????????????,??????????????????????
???,?????????。
犃.1.5?????????
犃.1.5.1???????????
???????,??犚2犡,??????????????????,???????????
??????。?????????狓
犻犼
??????狓^
犻犼
,犿????狓^1犼,狓^2犼,狓^3犼,…,狓^
犿犼
????
狓犼,?犚2犡??(A.18)????,??????犚2犡cum??(A.19)????:
犚2犡=1-RSS
SSX=1-
∑
犿
犻=1∑
狀
犼=1(
狓
犻犼
-狓^
犻犼
)
2
∑
犿
犻=1∑
狀
犼=1(
狓
犻犼
-狓犼)
2
……(A.18)
犚2犡cum=∑
犃
犪=1(
犚2犡)犪…………(A.19)
21
犌犅/犜37969—2019
??:
SSX———???????????,??????????????????,??∑
犿
犻=1∑
狀
犼=1(
狓
犻犼
-狓犼)
2;
RSS———??????????,??∑
犿
犻=1∑
狀
犼=1(
狓
犻犼
-狓^
犻犼
)
2。
?犚2犡????,RSS??,犚2犡???,?????????????,?????????
?。????犃???????,??,??????????????????????????
????。?????????,???????,??犚2犡???,???????,??????
????????????????。??,?SIMCA????,???????????????
???????????????。
犃.1.5.2???
??????????(?狆??狇?)??????,????????,?????,????
??????????。狆??狇??????犇狆狇(?犇狇狆)??(A.20)????:
犇狆狇=犇狇狆=
犙2狆狇+犙2狇狆
犙2狆+犙2狇槡
-1…………(A.20)
??:
犙2狆狇———狇??????狆????????????;
犙2狇狆———狆??????狇????????????;
犙2狆———狆?????????;
犙2狇———狇?????????。
?????,??????????,???????????,??????????????
?。???????????????????,???????????3。
犃.1.5.3?????????
??????????,???????????????(???)????????????
??,??????????????????????,??,??????????,??????
????????????,?????????100%???。??,?????????????
??????????,??????????????????????????????,???
????????????????。
??,?????????????———????(confusionmatrix)????????????
?????????????,????????????。
犃.1.6??????
?????????????,???????????,?????????????????
???????,???????????,?????。??,??????。
犃.1.7??
?SIMCA??????????????????,??????????????。???
???,???犉???,????????5%?1%,??????????????,?????
??????????????。
犃.1.8??犛犐犕犆犃??????
??SIMCA??????????:
31
犌犅/犜37969—2019
a)???????????????,????、??????;
b)?????????PCA??;
c)?????????,????、????,??PCA??????????;
d)?????????;
e)??b)~d),??????????。
犃.2犘犔犛犇犃????
犃.2.1犘犔犛犇犃????????
PLSDA?????????????????????????????,????????
?,?????????(???)??,??????????1,??????0?????。??
????????????PLS??,??PLSDA???,????????????????。
犃.2.2犘犔犛犇犃??????
???犿????????????犡犿×狀?,??犃,犅,犆,…,犖???,?????????
??????,?犿?????????????,?????,?????1,??????0,??,
?1?0?????????犢犿×犖??,??(A.21):
犢犿×犖=
犃?犅?犖?
10…00
10…00
10…00
01…00
01…00
01…00
00…01
00…01
00…01
熿
燀
燄
燅
烍
烌
烎
犃?
烍
烌
烎
犅?
烍
烌
烎
犖?
…(A.21)
?犡犿×狀?犢犿×犖??PLS????,??????,?????????????,??????
??????????,?????????,??(A.22)~(A.24):
犡=犜犘+犈犡…………(A.22)
犢=
犝犙
+犈犢
…………(A.23)
犝=犜犅…………(A.24)
??:
犜———犡犿×狀??????????;
犘———????;
犈犡———????;
犝———犢犿×犖??????????;
犙———????;
41
犌犅/犜37969—2019
犈犢———????;
犅———??????。
PLS?????,????????、???????SIMPLS???,?????????
??。
??????????犡un????,?犡un????????????犜un,??(A.25)???
???????????:
犢un=犜un
犅犙
…………(A.25)
????????????1,????0,??,?????????1,??????????
????????。??????????????(??狔)????,?????,???????
????????????,?????:①?狔>0.5,???<0.5?,????????;②?狔<
0.5,??<0.5?,?????????;③?狔???≥0.5,?????。
???????????????犢犿×犖???犖?????,???(A.22)~?(A.24)???
????,?????(A.25)??????????,????????????。???????
????????、??????(????0,1,2,…,犖?????????)????????,?
?????PLSDA?????,????????????。
???PLSDA??????,??????????,????????????,?????
???,???????????????????,??????PLSDA?????????
??。
犃.2.3???????
???????PRESS?????????????,????????????????,?
???????????????????、??????????PRESS??????????
??。??PLSDA???,????????????????PLS????。????????
??PRESS?,?????????????????,???????(???????????
??)、???????CV2?。??PRESS???????????????????PCA??
??????????????,??A.1.2。
???PLSDA???????,???????????PRESS?????????,???
?犉?????PRESS犃?PRESS(犃+1)??????????????????,???,?
PRESS犃
PRESS(犃-1)≤0.95
2?,
???(A.9)???,CV2≥0.0975,??????,????????????
?;??,?CV2<0.0975?,??????,???????????????,????????
?,???????????。
犃.2.4??????????
????A.1.3???????????、????????,???PLSDA????????
???,??????????????????????????(?狔>0.5,???<0.5?)?,
??????????。
????????????,??PLS????????????????????,????
??????????????,?????????。
犃.2.5犘犔犛犇犃??????
犃.2.5.1犘犔犛犇犃????????
????(犚2,determinationcoefficient)????????????????,????????
51
犌犅/犜37969—2019
?????????。??狔^犻??????(??犖???)????,狔^1,狔^2,…,狔^犖????狔,狔犻
????????(???1),???????(A.26)????:
犚2=犛SSR
犛SST=犛
SST-犛SSE
犛SST
=∑
犖
犻=1(
狔^犻-狔)
2
∑
犖
犻=1(
狔犻-狔)
2
=1-∑
犖
犻=1(
狔^犻-狔犻)
2
∑
犖
犻=1(
狔犻-狔)
2
……………(A.26)
??:
犛SST———???????????,??∑
犖
犻=1(
狔犻-狔)
2;
犛SSR———??????????,??∑
犖
犻=1(
狔^犻-狔)
2;
犛SSE———??????????,??∑
犖
犻=1(
狔^犻-狔犻)
2。
??,犛SST=犛SSR+犛SSE。
?犚2????,犛SSR?犛SSE??,犚2???,??????????。犚2?????0~1。??
??犃???????,??,?????????????????????????????,?
????????(A.27)????:
犚2=犚2犢cum=∑
犃
犪=1(
犚2犢)犪…………(A.27)
??????????,犚2?????,??????????????????1。??,??
?????????,????????,?????,犚2????;??????????,??犚2
??1,?????????????,???????。??,????????????????
???????????。
犃.2.5.2???????
???PLSDA???????????,???????(PRESS)????????????
??,?????????????????????。?????,??????????????
??1,??????犖?????,???????????狔^cv犻??,??,??????????
??PRESS??(A.28)??:
PRESS=∑
犖
犻=1(
狔^cv犻-1)
2
…………(A.28)
??,?????????,????????????????????1,PRESS????,
???????????????????。
???????????,???PRESS?????。??,???PRESS???????,?
?????????。
犃.2.5.3?????????
???PLSDA???????,????????????(?狔>0.5,???<0.5?)???
????????????,??,PLSDA??????????100%。???????????
?100%,????????????,??????????????????????????
?,????????????,????????????????????????????
??。
犃.2.6??????
????A.1.6。
61
犌犅/犜37969—2019
犃.2.7??
?PLSDA??????????????,??A.2.2????????,?????????
?????。
犃.2.8??犘犔犛犇犃??????
??PLSDA??????????:
a)?????????????????,????、??????;
b)??PLSDA?????;
c)???????????,????、????,??PLSDA??????????;
d)??PLSDA???????。
犃.2.9??犛犐犕犆犃?犘犔犛犇犃?????????
??SIMCA?PLSDA?????????PCA?????????,??????????
?????,????????????????????,???????????,??????
?????????,???????PRESS,CPV,???(???)???????????,??
????????????。??,??????3?,CPV?????85%,???????15?,
?????????,??????????15??,????????????2~3?????。
???????,????????????,?????????????????,????
??????????,????????????,??SIMCA????????。?????
?,????PLSDA??????????,??????PLSDA???,PLSDA??????
????????????、?????????????。
????????????????????????????????,????????、?
?????????,?????????????????,?????/??(2D/3D)?????
???????,?????????。
71
犌犅/犜37969—2019
??犅
(?????)
犉??????
犉????????B.1??B.2。
?犅.1犉??????犘[犉(狀1,狀2)>犉犪(狀1,狀2)]=α=0.05
狀2
狀1
1234567891012152024304060120∞
1161.4199.5215.7224.6230.2234.0236.8238.9240.5241.9243.9245.9248.0249.1250.1251.1252.2253.3254.3
218.5119.0019.1619.2519.3019.3319.3519.3719.3819.4019.4119.4319.4519.4519.4619.4719.4819.4919.50
310.139.559.289.129.018.948.898.858.818.798.748.708.668.648.628.598.578.558.53
47.716.946.596.396.266.166.096.046.005.965.915.865.805.775.755.725.695.665.63
56.615.795.415.195.054.954.884.824.774.744.684.624.564.534.504.464.434.404.36
65.995.144.764.534.394.284.214.154.104.064.003.943.873.843.813.773.743.703.67
75.594.744.354.123.973.873.793.733.683.643.573.513.443.413.383.343.303.273.23
85.324.464.073.843.693.583.503.443.393.353.283.223.153.123.083.043.012.972.93
95.124.263.863.633.483.373.293.233.183.143.073.012.942.902.862.832.792.752.71
104.964.103.713.483.333.223.143.073.022.982.912.852.772.742.702.662.622.582.54
114.843.983.593.363.203.093.012.952.902.852.792.722.652.612.572.532.492.452.40
124.753.893.493.263.113.002.912.852.802.752.692.622.542.512.472.432.382.342.30
134.673.813.413.183.032.922.832.772.712.672.602.532.462.422.382.342.302.252.21
144.603.743.343.112.962.852.762.702.652.602.532.462.392.352.312.272.222.182.13
154.543.683.293.062.902.792.712.642.592.542.482.402.332.292.252.202.162.112.07
164.493.633.243.012.852.742.662.592.542.492.422.352.282.242.192.152.112.062.01
174.453.593.202.962.812.702.612.552.492.452.382.312.232.192.152.102.062.011.96
184.413.553.162.932.772.662.582.512.462.412.342.272.192.152.112.062.021.971.92
194.383.523.132.902.742.632.542.482.422.382.312.232.162.112.072.031.981.931.88
204.353.493.102.872.712.602.512.452.392.352.282.202.122.082.041.991.951.901.84
214.323.473.072.842.682.572.492.422.372.322.252.182.102.052.011.961.921.871.81
224.303.443.052.822.662.552.462.402.342.302.232.152.072.031.981.941.891.841.78
234.283.423.032.802.642.532.442.372.322.272.202.132.052.011.961.911.861.811.76
244.263.403.012.782.622.512.422.362.302.252.182.112.031.981.941.891.841.791.73
254.243.392.992.762.602.492.402.342.282.242.162.092.011.961.921.871.821.771.71
264.233.372.982.742.592.472.392.322.272.222.152.071.991.951.901.851.801.751.69
274.213.352.962.732.572.462.372.312.252.202.132.061.971.931.881.841.791.731.67
284.203.342.952.712.562.452.362.292.242.192.122.041.961.911.871.821.771.711.65
294.183.332.932.702.552.432.352.282.222.182.102.031.941.901.851.811.751.701.64
304.173.322.922.692.532.422.332.272.212.162.092.011.931.891.841.791.741.681.62
404.083.232.842.612.452.342.252.182.122.082.001.921.841.791.741.691.641.581.51
604.003.152.762.532.372.252.172.102.041.991.921.841.751.701.651.591.531.471.39
1203.923.072.682.452.292.182.092.021.961.911.831.751.661.611.551.501.431.351.25
∞3.843.002.602.372.212.102.011.941.881.831.751.671.571.521.461.391.321.221.00
81
犌犅/犜37969—2019
?犅.2犉??????犘[犉(狀1,狀2)>犉犪(狀1,狀2)]=α=0.01
狀2
狀1
1234567891012152024304060120∞
14052499954035625576458595928598160226056610661576209623562616287631363396366
298.5099.0099.1799.2599.3099.3399.3699.3799.3999.4099.4299.4399.4599.4699.4799.4799.4899.4999.50
334.1230.8229.4628.7128.2427.9127.6727.4927.3527.2327.0526.8726.6926.6026.5026.4126.3226.2226.13
421.2018.0016.6915.9815.5215.2114.9814.8014.6614.5514.3714.2014.0213.9313.8413.7513.6513.5613.46
516.2613.2712.0611.3910.9710.6710.4610.2910.1610.059.899.729.559.479.389.299.209.119.02
613.7510.929.789.158.758.478.268.107.987.877.727.567.407.317.237.147.066.976.88
712.259.558.457.857.467.196.996.846.726.626.476.316.166.075.995.915.825.745.65
811.268.657.597.016.636.376.186.035.915.815.675.525.365.285.205.125.034.954.86
910.568.026.996.426.065.805.615.475.355.265.114.964.814.734.654.574.484.404.31
1010.047.566.555.995.645.395.205.064.944.854.714.564.414.334.254.174.084.003.91
119.657.216.225.675.325.074.894.744.634.544.404.254.104.023.943.863.783.693.60
129.336.935.955.415.064.824.644.504.3
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