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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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)??。

???????:???????????、??????、????、?????????、??

?????????、???????????、?????????????、????????、?

?????、?????????、????(??)??????、????????????、???

???????????、???(??)??????。

??????:???、???、???、??、???、???、???、???、???、???、

??、???、???、??、???、???、???、???、??、???、???、???、??、

???、???、???、??、???。

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

?????????、????????????,?????????。

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)?

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?。

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。

犌犅/犜37969—2019

?1??????????????

10???????

10.1????????,

??????????????????(???、????)??????

???????,?????????????????,???????。

10.2????????,

????:??、??、MSC?SNV?。???????????????

?,?????????????;????????,????????;MSC?SNV??????

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??????????,

?????????????????;??????????,??

?????????????????。??,??????????????。?????,???

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)??????????,???????????、????、?????;

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。

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

…………(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)????:

犪=1Var

(犉犪)=∑

犪=1λ

…………(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????????????[∑

犪=1Var

(犉犪)]??????

?(∑

犼=1犙

犼)

???,????????????(cumulativepercentvariance,CPV,???????)

???犃????犉1,犉2,……,犉犃?????????????????,CPV犃??(A.4)??

??:

CPV犃=∑

犪=1Var

(犉犪)

犼=1犙

犪=1λ

犼=1犙

…………(A.4)

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^

犻犼

+犲

犻犼

=狓狇犼+∑

犃狇

犪=1

犻犪狆

犪犼

+犲

犻犼

……(A.6)

??:

狓狇

犼———?狇???犼???;

狓^狇

犻犼

———???????狓狇

犻犼

?????,??∑

犃狇

犪=1

犻犪狆

犪犼

犃狇———?狇?????????;

犻犪———?狇????犻??犪?????????;

狆狇

犪犼

———?狇????犼??犪?????????;

犻犼

———?狇????犻???犼????,??(狓

犻犼

-狓^

犻犼

)。

???????,??????????????,?????????????,??????

?,???????????????????????????;???????????????

???????????,?????????????。??????????????????

????、???????????,??????。??????,??????????????,

??????????,????,??????????。??,????????????,???

?????????,????????,??????,????????????????,???

?SIMCA?????????。

犃.1.3???????

?????????犃???????????????。???????????????

?????。??,??????????,??????????,?????,?????????

??。??????????,?????????????,?????,????????,???

??????????????????????。???????????????????,?

??????(crossvalidation)??????????????????。????????,??

?????????(?????????)?,???????????????????????。

?????????????,????????????????,??????????????

?????????。??,??????????????????PRESS(predictiveresidual

errorsumofsquares)??(A.7)????:

PRESS=∑

犻=1∑

犼=1

犻犼

=∑

犻=1∑

犼=1(

犻犼

-狓^

犻犼

……(A.7)

?????????????,??????????????,???????????,??

01

犌犅/犜37969—2019

?????????????????????????。??????????????,???

?????????,???????????????,??PRESS?。??????????,

??????,??????????????PRESS?,????????????。?PRESS

?????????????????,???犉?????PRESS犃?PRESS(犃+1)???????

??,???犉???????(A.8)??:

犉=

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)

()

…………(A.9)

CV

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=∑

犪=1狋

犻犪

狋犪

…………(A.11)

??:

狋犻犪———?犻???????犪????????。

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=∑

犼=1

犻犼

狀-犃狇

…………(A.14)

??:

犻犼

———?狇???犻???犼????。

犃狇———?狇??????。

??,??犿??????????狇?,????????,??犙2,?犙2??(A.15)??

??:

犙2=∑

犻=1∑

犼=1

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

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-

犻=1∑

犼=1(

犻犼

-狓^

犻犼

犻=1∑

犼=1(

犻犼

-狓犼)

……(A.18)

犚2犡cum=∑

犪=1(

犚2犡)犪…………(A.19)

21

犌犅/犜37969—2019

??:

SSX———???????????,??????????????????,??∑

犻=1∑

犼=1(

犻犼

-狓犼)

2;

RSS———??????????,??∑

犻=1∑

犼=1(

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

犃?

犅?

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

=∑

犻=1(

狔^犻-狔)

犻=1(

狔犻-狔)

=1-∑

犻=1(

狔^犻-狔犻)

犻=1(

狔犻-狔)

……………(A.26)

??:

犛SST———???????????,??∑

犻=1(

狔犻-狔)

2;

犛SSR———??????????,??∑

犻=1(

狔^犻-狔)

2;

犛SSE———??????????,??∑

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=∑

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=∑

犻=1(

狔^cv犻-1)

…………(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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