Talanta 104 (2013) 5866

Contents lists available at SciVerse ScienceDirect

Talanta
journal o!e"a#e$ %%%&elsevier&co!'locate'talanta
C()*
n
a
n
b
n
color s"ace "re+ictive !o+els ,or colori!etr- +evices .nal-sis o,
"er,u!e /ualit-
0abia 1ori,i
a2b2n
2 3veline *e Dre4au
a
2 5ean67ranc6ois .ntinelli
b
2 0obert Valls
a
2 8atalie Du"u-
a
a
*aboratoire *(S.2 ). 4692 )/ui"e :)T(C.2 Case 4512 .i;6:arseille <niversite42 133=9 :arseille Ce+e; 202
7rance
b
.nal-tics Consultin#2 22 >arc *ubonis 06000 8ice2 7rance
a r t i c l e i n , o
.rticle istor-$
0eceive+ 21 :a- 2012 0eceive+ in revise+ ,or! 8 8ove!ber 2012
.cce"te+ 11 8ove!ber 2012 .vailable online 23 8ove!ber 2012
1e-%or+s$
Colori!etr-
S"ectro"oto!etr-
C()*.?
>re+ictive !o+els
@ualit- control
7ra#rances
a b s t r a
c t
Color
"erce"tion
"la-s a
!ajor role in
te
consu!er
evaluation o,
"er,u!e
/ualit-&
Consu!ers
nee+ ,irst to
be entirel-
satis,ie+
%it te
sensor-
"ro"erties o,
"ro+ucts2
be,ore oter
/ualit-
+i!ensions
beco!e
relevant&
Te
evaluation o,
co!"le;
!i;tures
color
"resents a
callen#e
even ,or !o+ern anal-tical tecni/ues& . variet- o,
instru!ents are available ,or color !easure!ent&
Te- can be classi,ie+ as tristi!ulus colori!eters
an+ s"ectro"oto!eters& Absolescence o, te
electronics o, ol+ tristi!ulus colori!eter arises
,ro! te +i,,icult- in ,in+in# re"air "arts an+ lea+s
to its re"lace!ent b- !ore !o+ern instru!ents&
Bi# /ualit- levels in color !easure!ent2 i&e&2
accurac- an+ reliabilit- in color control are te
!ajor a+vanta#es o, te ne% #eneration o, color
instru!entation2 te inte#ratin# s"ere
s"ectro"oto!eter& T%o !o+els o,
s"ectro"oto!eter %ere teste+ in trans!ittance
!o+e2 e!"lo-in# te +'01 #eo!etr-& Te
C()*
n
a
n
b
n
color s"ace "ara!eters %ere !easure+
%it eac instru!ent ,or 380 sa!"les o, ra%
!aterials an+ bases use+ in te "er,u!e
co!"ositions& Te results %ere #ra"icall-
co!"are+ bet%een te colori!eter +evice an+ te
s"ectro"oto!eter +evices& .ll color s"ace
"ara!eters obtaine+ %it te colori!eter %ere
use+ as +e"en+ent variables to #enerate
re#ression e/uations %it values obtaine+ ,ro! te
s"ectro"oto!eters& Te +ata %as statisticall-
anal-Ce+ to create "re+ictive !o+el bet%een te
re,erence an+ te tar#et instru!ents trou# t%o
!eto+s& Te ,irst !eto+ uses linear re#ression
anal-sis an+ te secon+ !eto+ consists o, "artial
least s/uare re#ression (>*S) on eac co!"onent&
D 2012 )lsevier
?&V& .ll ri#ts
reserve+&
1& (ntro+uction
Color o, ,oo+s2 ,ra#rances an+
cos!etics is te ,irst contact "oint o, te
cons
u!e
r
%it
it2 so
it
stro
n#l-
in,luences consu!ersE
"re,erences& Color as a
!ajor role in te
acce"tabilit- o, te "ro+uct
an+ is relate+ to te
consu!er "erce"tion o,
,lavor2 s%eetness2 scents
an+ oter "-sical
"ro"erties in relation
to te /ualit- o, te
"ro+uct F1 4 G&
:anu,acturers ave
been a%are o, tis
,or a lon# ti!e2
%ic e;"lains teir
e,,orts to assess an+
control te color o,
teir "ro+ucts& Since
te "erce"tion o,
color !ainl-
+e"en+s o, te
observer an+ oter
illu!ination con+i6
tions2 an objective assess!ent o, color
re/uires a""ro"riate instru!entation tat
,ollo%s te reco!!en+ations institute+ b-
te C() ((nternational Co!!ission on
(llu!ination)& Consu!er coice +e"en+s on
te /ualit- o, te "ro+uct2 te color as
suc a
n
Corres"on+in# autor at$ *aboratoire *(S.2
)/ui"e :)T(C. ). 46922 Case 4512 .i;6:arseille
<niversite42 Ca!"us +e St 5e4ro!e2H .venue
)sca+rille 8or!an+ie 8ie!en2 133=9 :arseille
Ce+e; 202 7rance&
)6!ail a++resses$ rabia&Iori,iJ-aoo&,r
(0& 1ori,i)2 -veline&le6+reauJuniv6 a!u&,r (3&
*e Dre4au)2 j,antinelliJanal-tics6consultin#&,r
(5&67& .ntinelli)2 natalie&+u"u-Juniv6a!u&,r (8&
Du"u-)&
003=6=140'K 6 see ,ront !atter D 2012
)lsevier ?&V& .ll ri#ts reserve+&
tt"$''+;&+oi&or#'10&1016'j&talanta&2012&11&
026
"s-c
olo
#ical
i!"
act
on
te
cons
u!e
r
tat
it is
+ire
ctl-
asso
6
ciate
+ to
te
/uali
t- o,
te
"ro+
uct&
Tu
s2
te
i!"l
e!e
ntati
on
o,
instr
u!e
ntal
!ea
sure
!en
ts o,
colo
r ,or
te
/uali
t-
cont
rol is
corr
elat
e+
to
te
cons
u!e
r
coi
ce
F5
=G&
(
n
te
case
o,
te
crea
tion
o,
"er,
u!es2 one o, te !ost
current "-sicoce!ical
anal-sis assure+ b- te
control laborator- is te
color !easure!ent o, ra%
!aterials2 bases an+
"ro+ucts& Te en#ineerin#
"ro"erties F10G o,
"er,u!es are i!"ortant2 i,
not essential2 in te
"rocess +esi#n an+
!anu,acture o, "er,u!e
"ro+ucts& Color2 #loss an+
translucenc- are te
o"tical "ro"erties tat
coul+ be vie%e+ b- te
consu!er as an as"ect o,
te #lobal /ualit-&
>er,u!ers ave to !atc
te "ro+uct /ualit- %it
s"eci,ic re/uire!ents o,
te consu!er an+ te
,ee+bacI obtaine+ b-
!arIet researc tools&
7ro! te earl- 1=80s
to te en+ o, te 1==0s2
te colori!eter use+ ,or
"er,u!ers consists in a
+evice %it tree sensors
,iltere+2 %ic #ive te
relative a!ounts o, te
tree "ri!ar- colors
re/uire+ ,or a color !atc2
re+2 #reen an+ blue&
Bo%ever2 because o, its
+iscontinuation o,
tecnical su""ort an+
re"air "arts2 tis +evice
beca!e obsolete& 7ro!
no% on2 te colori!eter
consists in a !o+ern
e/ui"!ent !ore available
on te !arIet2 an
inte#ratin# s"ere
s"ectro"oto!eter %it
!ulticannel +etector& Te
0& 1ori,i et al& ' Talanta 104 (2013) 5866 5=
bene,it o, tis ne% #eneration o, +evice lies in its
lon#6ter! stabilit-2 in contrast to ,ilter +evice2 no
alteration "eno!enon is observe+& Tis
instru!entation %it i!"rove+ sensor tecnolo#-
allo%s a !ore accurate an+ re"ro+ucible
+eter!ination o, te color s"ace "ara!eters F11G &
To objectivel- +e,ine a color2 in a++ition to usin#
a""ro"riate instru!entation2 it is necessar- to ,ollo%
te reco!!en+ations establise+ b- te C()& Te
C() reco!!en+s a "articular illu!i6nant'observer
co!bination an+ color s"aces (C()L3M2 C()*
n
a
n
b
n
)
"ur"ose+ at stan+ar+iCe te +e,inition o, color an+
"rovi+e !ore uni,or! color +i,,erences in relation to
visual +i,,erences&
Te /ualit- control is te %a- to control "rocess
variation ,or assurin# te "ro+uction /ualit- a#ainst
+esi#n tolerances& (t is base+ on te lar#e a!ount
o, +ata collecte+ over ti!e %it te re,erence
instru!ent2 te tristi!ulus colori!eter +evice& 7ro!
tese +atabase2 tolerances ave been +e,ine+ on
eac t-"e o, "ro+ucts ,or te tree C() color s"ace
"ara!eters *
n
2 a
n
an+ b
n
& Control !a"s ave been
create+ ,ro! te tolerances2 tou# tese control
!a"s are +evice6s"eci,ics& Tus2 %en usin# a ne%
+evice2 te !easure+ *
n
a
n
b
n
"ara!eters are not
e;actl- te sa!e2 so it is e;clu+e+ to use te sa!e
control !a"s ,or te /ualit- control& Ten2 it
beco!es necessar- to #o to establis correlations
bet%een !easure!ents !a+e on +i,,erent +evices
in or+er to continue usin# te sa!e car+ control& (n
teor-2 tere soul+ not be an- +i,,erences bet%een
te results obtaine+ b- colori!etr- an+ b-
s"ectro"oto!etr-& Bo%ever2 in "ractice2 +es"ite te
,act tat %orIin# "ro"erl- %it bot t-"es o,
instru!ents %ell calibrate+2 +i,,erences in res"onses
a,,ect te "rocess o, /ualit- control& Tese
+i,,erences a,,ect even !ore te sa!"les subjecte+
to s!all tolerance ran#es tan tose subject to
#reater tolerance ran#es& (n+ee+2 in te case o,
s!all ran#es o, tolerances2 +i,,er6ences %ill result in
an easier "assa#e in non6con,or!it- o, te sa!"le2
"reviousl- teste+ in accor+ance %it te re,erence
!eto+& 7ro! a "urel- "ractical "oint o, vie%2 te
in+ustrial is intereste+ to ave2 ,ro! is ne% +evice2
te sa!e bacI line tat %it is ,or!er +evice& Te
#oal is to !aintain its +atabase ac/uire+ over 25
-ears&
Tere are ,e% scienti,ic "ublications on
correlations bet%een !easure!ents& ?usli# F12G
%orIe+ on te co!"arison o, a tristi!ulus
colori!eter an+ a s"ere s"ectro"oto!eter ,or te
!easure!ent o, oran#e juice color b- tristi!ulus
L3M values correlation& 7ullerton an+ 1ei+in# F13G
!a+e a co!"arison bet%een a tristi!ulus
colori!eter an+ t%o s"ectro"oto!eters ,or te
anal-sis o, sIin color b- *
n
a
n
b
n
"ara!eters
correlation& (n te t%o stu+ies2 te !easure!ents
%ere !a+e b- re,lectance !o+e2 %ic is in
accor+ance to te C() stan+ar+s ,or o"a/ue
sa!"les& Te results are tat satis,actor- correlation
coe,,icients %ere establise+ b- re#ression anal-sis&
8everteless2 tese stu+ies onl- re,er to re,lectance
!o+e ,or o"a/ue sa!"les %ile !an- "ro+ucts
re/uirin# color !easure!ent suc as ra% !aterials
,or "er,u!es are trans"arent an+
re,lectance !o+e is not suitable ,or tis
+eter!ination& 7urter!ore2 a revie%
on instru!ental !easure!ent o,
oran#e juice color F14G states tat it
%as +e!onstrate+ tat color
!easure!ent b- trans!ission %as not
e,,ective +ue to its lacI o,
re"ro+ucibilit-&
(n tis stu+-2 t%o benc6to"
s"ectro"oto!eters ave been teste+N
tese instru!ents are +esi#nate+ as
tar#ets instru!ents& Te coice o, te
s"ectro"oto!eters as been +one
accor+in# to a set o, s"eci,ications
#aterin# te necessar- tecnical
,eatures ,or a s"ectro"oto!eter&
Su""liers %ere contacte+ to coose te
s"ectro"oto!eter tat best !eets
tese criteria& Tese selection criteria
%ere2 a!on# oters2 te t-"es o,
illu!inants2 te !ea6sure!ent ti!e2 te
siCe o, sa!"le cell su""orte+2 te color
s"aces available ,or te calculation2
an+ ,inall- a ver- i!"ortant "oint2 te
access to s"ectral curves an+ to
inte#rals values& Several
s"ectro"oto!eters o, +i,,erent bran+s
ave been selecte+
an+ te ,inal coice %as +one
accor+in# to teir availabilit- ,or rental&
7or +irect co!"arison bet%een te
colori!eter an+ te s"ec6
tro"oto!eters +evices2 results %ere
!easure+ in C()*
n
a
n
b
n
color s"ace&
Te ai! o, tis stu+- is to be able to
"re+ict ,ro! te !easure+ values o,
te tar#et instru!ents2 te *
n
a
n
b
n
values tat %oul+ ave been obtaine+
on te re,erence instru!ent in or+er to
Iee" te current control !a"s& 7or tis2
te "roce+ure is to establis te best
"re+iction !o+el bet%een te re,erence
instru6!ent an+ te tar#et ones&
2& Teor-
2&1& ?asic color conce"ts
2&1&1& Oat is colorP
Te notion o, color is base+ on
tree criteria$ te ue (sa+e)2 te
li#tness (bri#tness) an+ te
saturation (intensit-)& Tese tree
ele!ents are te tree color attributes2
an+ can be "ut to#eter to create te
tree6+i!ensional color soli+ so%n in
7i#& 1(a) F15G &
(n te construction o, te tree6
+i!ensional soli+2 ues are te outer
ri! o, te soli+2 li#tness increases or
+ecreases alon# te vertical a;is an+
saturation varies accor+in# to te
central "oint& Value scales %ere
create+ to +e,ine tese criteria2 !an-
!eto+s ave been +evelo"e+ to
/uanti,- color an+ to allo% to e;"ress it
%it #reater ease an+ "recision&
2&1&2& S"ace ,or !easurin# color
Several s-ste!s ,or e;"ressin#
color nu!ericall- %ere +evel6o"e+ b-
an international or#aniCation concerne+
%it issues o, li#tin# an+ color2 te
(nternational Co!!ission on
(llu!ination (C())& Ane o, te best
Ino%n o, tese s-ste!s is te *
n
a
n
b
n
color s"ace (also re,erre+ to as
C()*.?) +evise+ in 1=96 F16G & (n tis
s"ace as seen in 7i#& 1 (b)2 *
n
in+icates li#tness2 its value e;ten+e+
,ro! 0 (blacI) to 100 (%ite)& a
n
an+ b
n
are te cro!aticit- coor+inates& Te
a
n
an+ b
n
in+icate color +irections$ Qa
n
is te re+ +irection2 a
n
is te #reen
+irection2 Qb
n
is te -ello% +irection2
an+ b
n
is te blue +irection& Te center
is acro!atic2 as te a
n
an+ b
n
values
increase an+ te "oint !oves out ,ro!
te center2 te saturation o, te color
increases&
Te color is re"resente+ b- a "oint
in tis s"ace2 %ic allo%s i#
"recision in te +e,inition o, tis one& Te values o,
*
n
2 a
n
2 an+ b
n
are "ro"ortional to te tristi!ulus
values L3M F19G an+ to Ln2 3n an+ Mn2 %ic are
te tristi!ulus values L3M o, a "er,ect re,lectin#
+i,,user2 set b- te C() in 1=312 as seen in te
trans,er )/s& (13)&
*
n
R

116

3
1
S
3
16
3
an R 500
"
L
1
S
3
3 1
S
3
#
b
n
R

200
"
3
1
S
M
1
S
3n
M
n
#
2&2& >rinci"le o, colori!etr-
Te "rinci"le o, colori!etr- is base+
on te tristi!ulus !eto+ F18G 2 i&e&2
eac color is te co!bination in
+i,,erent "ro"ortions o, re+2 #reen an+
blue& 7or one color2 te colori!eter
#ives te "ercenta#es o, te tree
"ri!ar- colors& . set o, tree sensors
,iltere+ to ave nearl- te sa!e color
sensitivit- as te u!an e-e2 receive
li#t ,ro! te object an+ trans!it te
60 0& 1ori,i et al& ' Talanta 104 (2013) 5866
Oite
+
Bue
Bi#
Lightness
*o%
Bi#

*o%

Bi#
Satura
tion
*i
#
tn
es
s
an
+
sa
tur
ati
on
+ b
- a
=
H
u
e
?
l
7i#& 1& (a) Creation o, tree6+i!ensional color
soli+N (b) C()*.? color s"ace& (7or inter"retation
o, te re,erences to color in tis ,i#ure le#en+2
te rea+er is re,erre+ to te %eb version o, tis
article)&
2
0
0
1
8
0
1
6
0
(%)
1
4
0
1
2
0
Reflectance
1
0
0
8
0
6
0
4
0
2
0
0
360
Wavelength (nm)
2
0
0
1
8
0
(
%
1
6
0
1
4
0
1
2
0
R
e
1
0
0
8
0
6
0
4
0
2
0
0
4
0
(

) 1
2
0
1
0
0
8
0
6
0
4
0 Y
2
0
0
36
0
4
1
0
4
6
0
2
0
0
1
8
0
z ()
1
6
0
1
4
0
1
2
0
1
0
0
8
0
6
0
4
0
Z
2
0
0
360 410 460 510 560 610 660 910 960
Wav
elen
gth
(nm) 7i
#&
2&
D
e
,unctions ;(l)2 -(l)2 C(l)
corres"on+in# to te u!an e-e
"erce"tion& (7or inter"retation o,
te
re,erenc
es to
color in
tis
,i#ure
le#en+2
te
rea+er
is re,erre+ to te %eb version o,
tis article)&
in,or!ation to te
+ata "rocessor
tat +eter!ines
te tristi!ulus
values L3M b- te
stan+ar+s o, te
C()&
2
&
s
"
e
c
t
r
o
"

o
t
o
!
e
:
u
nsors receive li#t
,ro! te object an+
trans!it te
in,or!ation to te
!icro"rocessor& 7or
eac %avelen#t
in te
visibl
e
li#t
ran#e
2 te
s"ect
ral
re,lec
tanc
e is
!ea
sure
+
F1=G&
7ro
!
te
s"e
ctral
+ata2
te
tristi
!ulu
s
valu
es
L3M
are
calc
ulate
+ b- inte#ration& L3M
tristi!ulus values are
e/ual to te
inte#ration o, te
sa+e+ areas in te
s"ectral re,lectance
curve o, te object (
7i#& 2)& (n a++ition to
+is"la- nu!erical
color +ata2 a
s"ectro"
oto!et
er can
also
+is"la-
a #ra"
o, te
s"ectral
re,lectan
ce to
"rovi+e
!ore
+etaile+
in,or!ati
on about
te
nature
o, te
color&
0& 1ori,i et al& ' Talanta 104 (2013) 5866 61
3& :aterials an+ !eto+
3&1& Sa!"les
Tree un+re+ an+ ei#t- sa!"les %ere
!easure+ %it eac instru!ent& Te sa!"les
are ra% !aterials an+ bases use+ in te
"re"aration o, "er,u!es2 as %ell as ,inise+
"ro+ucts& Sa!"les are ,ille+ into a 10 !!
ticI an+ 5 c! lon# cell !a+e o, or+inar-
#lass& To eac cate#or- o, sa!"les
corres"on+s a tolerance ran#e ,or te
"ara!eters values *
n
a
n
b
n
& (, at least one value
is out o, ran#e2 te sa!"le is consi+ere+ as
non con,or!&
3&2& Tristi!ulus colori!eter vs
s"ectro"oto!eters
Te e;"eri!ental re,erence +evice2 te
1onica :inolta CT310 is a trans!ission
tristi!ulus colori!eter use+ to !easure trans6
"arent colors o, ,lui+s& Te li#tin# is "rovi+e+
b- a "ulse+ ;enon arc la!" usin# illu!inant
D65 F20G 2 te +etector consists o, tree
sensors corres"on+in# to te cones o, te
u!an e-e tat !easure te li#t re,lecte+
,ro! te sa!"le %it +i,,use illu!i6nation'01
vie%in# an#le #eo!etr- F21G & Ten te
tristi!ulus values are calculate+ b- te built6in
+ata "rocessor& T%o s"ectro6"oto!eters are
teste+2 te 1onica :inolta C:63600+ an+ te
Bunter*ab <ltraScan Vis& Te
s"ectro"oto!eters incor"orate s"ere o"tics
an+ ,our "ulse+ ;enon la!"s2 coverin# te
entire visible s"ectru!&
Te instru!ents are use+ in trans!ission
!o+e2 te li#t ,ro! te la!"s "asses trou#
a +i,,user2 illu!inatin# te interior sur,ace o,
te inte#ratin# s"ere& Te sa!"le is in+irectl-
illu!i6nate+ b- li#t re,lecte+ ,ro! te s"ere
%alls %it +i,,use illu!ination'01 #eo!etr-&
*i#t re,lecte+ ,ro! te sa!"le is +irecte+
trou# lens s-ste! to a +i,,raction #ratin#&
Te #ratin# +is"erses te s"ectru! an+
re,lects it trou# an inte#ratin# lens to a +ual
406ele!ents silicone "oto+io+e arra-s
+etector& Te s"ectral re,lectance o, te
sa!"le is !easure+ bet%een 360 an+ 940 n!
%it a resolution o, 10 n!& Te si#nals ,ro!
te +etector arra- are "rocesse+ b- a +ata
"rocessor to -iel+ te a""ro"riate color scale
values& Te instru!ents are controlle+ b- te
co!"u6ter %it te S"ectra:a#ic 8L
"ro"rietar- so,t%are ,or te C:63600+ an+
%it te )as-:atc @C "ro"rietar- so,t%are
,or te <ltraScan Vis&
S-ste!s %ere calibrate+ %it a %ite
calibration "late2 usin# illu!inant D65 be,ore
eac sa!"le anal-sis& Te area o, !easure6
!ent is 20 !! ,or te colori!eter2 19 !! ,or
te 1onica s"ectro6"oto!eter an+ 1= !! ,or
te Bunter*ab s"ectro"oto!eter& Te
+istance bet%een te sa!"le an+
te e;it %in+o% o, li#t is 1 c! ,or
CT310 colori!eter2 an+ 1&5 c! ,or
te bot s"ectro"ot6o!eters&
0esults %ere !easure+ in
C()*
n
a
n
b
n
units ,or +irect
co!"arison %it te analo#ous
colori!eter values& )ac sa!"le
%as !easure+ tree ti!es to
assess te re"eatabilit- o, te
!easure!ent an+ te "ossible
variations o, inte#rals& Te re"eat6
abilit- bein# al!ost "er,ect2 an
avera#e o, tese !easure!ents
%as +one& Te !easure!ent ti!e
is 2 s ,or te tree instru!ents an+
te ti!e interval bet%een t%o
!easure!ents is 3 s&
."art ,ro! tis2 it is o, vital
i!"ortance to +e,ine te correct
con+itions o, te !easure!ents2
not onl- te stan+ar+ observer an+
illu!inant establise+ b- te C()2
but also te arran#e!ent o, te
sa!"le2 relate+ to te #eo!etr- o,
te s-ste!2 te li#t source
intensit-2 an+ te blanI
!easure!ent2 a!on# oters&
Di,,erences o, res"onses bet%een
te t%o t-"es o, instru!ent can be
+ue to +i,,erences in taIin# te
%ite re,erence s"ectru!&
Bo%ever2 it is i!"ossible because
o, te tecnical constraints o, te
+evice to intercan#e te %ite
calibration "lates servin# as
re,erence %ite tat are uni/ue ,or
eac instru!ent&
3&3& Data "rocessin#
T%o !eto+s o, +ata
"rocessin# are teste+& Te ,irst
!eto+ uses si!"le linear
re#ression anal-sis to e;"lore an+
!o+el te ,unctional relation
bet%een te colori!eter *
n
a
n
b
n
s"ace color an+ te
s"ectro"oto!eter one& Ten te
re#ression !o+el is use+ to !aIe
"re+ictions&
Te secon+ !eto+ consist o,
create "re+ictive !o+els b- "artial
least s/uare re#ression (>*S) on
eac "ara!eter F22G & :ost
co!!onl- use+ in s"ectro!etric
anal-Ces2 >*S can be use+ to
"re+ict a set o, +e"en+ent
variables ,ro! a lar#e set o,
e;"lana6tor- variables ("re+ictors)
tat can be i#l- correlate+& >*S
is te !ost "o"ular !eto+ in te
literature because it usuall-
"rovi+es better results tat oter
!ulti"le re#ression !eto+s& Tis
su"er6vise+ anal-sis is base+ on
te relation bet%een te
re,lectance s"ectra an+ te *
n
a
n
b
n
"ara!eters o, te sa!"le&
Averla""in# o, te s"ectral
in,or!ation !a- be overco!e b-
usin# tis "o%er,ul
!ultico!"onent anal-sis& Te
!eto+ allo%s a so"isticate+
statistical a""roac usin# te ,ull
s"ectral re#ion rater tan one
s"ace color value& Te al#orit! is
base+ on te abilit- to
!ate!aticall- correlate s"ectral
+ata to a "ro"ert- !atri; o, interest
%ile si!ultaneousl- accountin#
,or all oter si#ni,icant s"ectral
,actors tat "erturb te s"ectru!&
(t is a !ultivariate re#ression
!eto+ tat uses te ,ull s"ectral
re#ion an+ is base+ on te use o,
latent variables& (ts construction is
+ivi+e+ into t%o sta#es& Te
calibration ste" allo%s to construct
te calibration e/uation2 i&e&2 te
!ate!atical !o+el tat
correlates te in"ut variables L
(re,lectance s"ectra) an+ te
res"onses 3 "re+ictin# (values o,
*
n
a
n
b
n
)& Te nu!ber o, latent
variables selecte+ ,or te >*S
!o+el %as obtaine+ b- ,ull cross
vali+ation on te calibration set2
allo%in# an unbiase+ esti!ate o,
te vali+ation error& Te "re+iction
ste" is te use o, te !o+el to
"re+ict te res"onse (3) o, anoter
batc o, sa!"les& Te 2 batces
o, sa!"les %ere as ,ollo%s$ 255
sa!"les ,or calibration2 selecte+
ran+o!l- into te ,ull ran#es o,
values2 an+ 125 sa!"les ,or te
"re+iction (25 sa!"les eac o, 5
batces o, sa!"les receive+)2 also selecte+ to
cover te entire ran#e o, values&
Te evaluation o, te errors in te
calibration is esti!ate+ b- co!"utin# te
stan+ar+ error o, calibration (S)C) ,or eac
"ara6!eter *
n
a
n
b
n
& Te calculation o, te S)C
is #iven b- te )/& (4)&
-
-
0
S
)
C i R 1
i
R
u
P
8 1 " !
u
t
%ere -i is te Ino%n value2 -
0
i is
te calculate+ value2 8 te nu!ber
o, sa!"les an+ " is te nu!ber o,
in+e"en+ent variables&
Te stan+ar+ error o, "re+iction
(S)>) #ives an esti!ation o, te
"re+iction "er,or!ance +urin# te
ste" o, vali+ation ()/& (5))&
v

S)>
R
P
: -
i
!
i R 1 :
uu
t
%ere : is te nu!ber o, sa!"les
in te "re+iction set& .noter
use,ul "ara!eter is te relative
error o, "re+iction
(0)>) tat so%s te "re+ictive
abilit- o, te !o+el2 so%n in )/&
(6)&
0)
> R
S
)
>
100 T6U -
%ere - is te !ean o, te Ino%n
values&
.s te S)> is a stan+ar+
+eviation2 te (S)>)
2
can be
consi+ere+ as a variance an+2 in a
,irst a""ro;i!ation2 can be
anal-Ce+ as suc& Te 7iser
Sne+ecor test allo%s a co!"arison
bet%een te "re+ictive /ualities o,
t%o !o+els %it (S)>)
2
0 te
s!allest
62 0& 1ori,i et al& ' Talanta 104 (2013) 5866
(S)>)
2
suc as te )/& (9)$
TS)>
U
2
o
R
c
TS)>
U
2
0
%ere 7c is te critical value
"rovi+e+ b- te 7iserSne+ecor
tables ,or te nu!ber o, +e#rees
o, ,ree+o! o, te S)>& Tis test
%ill be a""lie+ to co!"are te
"re+iction "er,or!ance o, te t%o
s"ectro"oto!eters&
Te "re+ictive abilit- o, te
!o+el soul+ also be e;"resse+
b- te s/uare o, correlation
coe,,icient (0
2
) also calle+
+eter!ination coe,,icient& Te
re#ression coe,,icients are te
nu!erical coe,,i6cients %ic
e;"ress te linI bet%een te
"re+ictor variations an+ te
res"onse variations&
Te ce!o!etric a""lications
%ere "er,or!e+ b- Te
<nscra!bler
s
version =&2
+evelo"e+ b- C.:A (Co!"uter
.i+e+ :o+ellin#2 Tron+ei!2
8or%a-)&
4& 0esults an+ +iscussion
Te ,irst anal-tical ste" is to
e;a!ine te +ata b- co!"arin#
te re,erence instru!ent +ata %it
tose o, te tar#et instru6!ents
an+ to +eter!ine te level o,
a#ree!ent bet%een te +ata
obtaine+ b- te t%o instru!ents&
Tree levels o, a#ree!ent e;ist$
e/uivalence2 co!!utabilit- an+
inco!"atibilit-& (, te results are
i+entical to te anal-tical
i!"recision close2 bot
instru!ents are e/uivalent an+
can be e;can#e+ %itout loss o,
accurac-& (, te results are
i+entical at te close tolerance2
te- are not strictl- e/uivalent2
instru!ents are sai+ co!!utable&
7inall-2 i, te- "ro+uce results tat
+i,,er !ore tan te allo%e+
tolerance ,or te "ara!eter2 te
instru!ents are inco!"atible&
.ccor+in# to ?lan+ an+ .lt!an
F23G2 te best statistical a""roac
is not obvious& Te usual !eto+
is to calculate te correlation
coe,,i6cient bet%een te t%o
instru!ents +ata2 but te use o,
correla6tion coe,,icient as an
in+icator o, a#ree!ent is not
su,,icient& (n tis stu+-2 teir
alternative a""roac base+ on
#ra"ical tecni6/ues is teste+ as
a !easurin# a#ree!ent& 7irst2 te
+ata is "lotte+ an+ a line
o, e/ualit- is +ra%n ( 7i#&
3)& Tis line re"resents
te i+eal case %ere te
t%o instru!ents #ave
e;actl- te sa!e results
,or eac sa!"le& (t el"s
to visuall- evaluate te
+e#ree o, a#ree!ent
bet%een te t%o
instru!ents& Ten2 te
re#ression lines are
+ra%n an+ te correlation
coe,,icients r are
calculate+ bet%een te
t%o instru!ents& 7or te
+ata in 7i#& 3 2 r*n R0&=62
ran R0&69 an+ rb
n
R0&=9&
Te -"otesis is tat
te !easure!ents b- te
t%o instru!ents are
linearl- relate+ ,or *
n
an+
b
n
but nor ,or a
n
& Tis
coul+ be e;"laine+ b-
te ,act tat *
n
is linearl-
relate+ to 3 ()/& (1)) an+
tat te "artici"ation o, M
in te calculation o, b
n
is
ver- lo% co!"are+ to 3 (
7i#& 3) so tat te )/& (3)
is nearl- a linear relation
o, 3& Bo%ever2 a
n
+e"en+s as !uc on L
tan on 3& Te lo%
correlation coe,,icient o,
a
n
alrea+- so%s a lacI
o, a#ree!ent& Tou#2
even i, te "ara!eters *
n
an+ b
n
so% i#
correlations2 tis +oes
not necessaril- !ean
tat te t%o
instru!ents are in
a#ree!ent& (n+ee+2 r is
+e,ine+ b- !easurin# te
stren#t o, a relation
bet%een t%o variables2
not te a#ree6!ent
bet%een te!& Tere is a
"er,ect a#ree!ent onl- i,
te "oints in 7i#& 3 lie
alon# te line o, e/ualit-2
but tere is a "er,ect
correlation i, te "oints
lie alon# an- strai#t lineN
tat is to sa- i, te
re#ression line is e/ual
to te line o, e/ualit-&
. use,ul start is to
+ra% a si!"le "lot o, te
results o, one instru!ent
a#ainst tose o, te oter
(as +one on 7i#& 3 ) but
usuall- te +ata "oints
%ill be clustere+ near te
re#ression line an+ it %ill
be +i,,icult to assess
bet%een6
s"ectro"oto!eter
+i,,erences& . "lot o, te
+i,,erence bet%een te
+ata o, te
s"ectro"oto!eters
a#ainst teir !ean !a-
be !ore in,or!ative& Te
+i,,erence in value
bet%een tar#et an+
re,erence is +e,erre+ in
or+inate an+ te avera#e
o, tese t%o values on
te abscissa& 7i#& 4
+is"la-s consi+erable
lacI o, a#ree!ent
bet%een te t%o
instru!ents2 %it
+iscre"ancies o, u" to 4
,or *
n
an+ 25 ,or b
n
&
Tese +i,,erences are
not obvious ,ro! 7i#& 3 &
7or te +ata2 tere is no
obvious relation bet%een
te +i,,erence an+ te
!ean& <n+er tese
con+itions2 te lacI o,
a#ree!ent can be
revie%e+ b- calculatin#
te bias2 esti!ate+ b-
te !ean +i,,erence +
(re,er6ence "ara!eter
!inus tar#et "ara!eter)
an+ te stan+ar+ +evia6
tion o, te +i,,erences s&
(, tere is a consistent
bias2 te values can be
a+juste+ b- subtractin# +
,ro! te +ata obtaine+
b- te tar#et instru!ent&
7or te *
n
+ata2 + is 1&1
an+ s is 0&6& 7or te b
n
+ata2 + is 3&1 an+ s is
5&0& Te +i,,erences are e;"ecte+
to lie bet%een te li!its o,
a#ree!ent +2s an+ +Q2s ( 7i#&
4)&Tese li!its o, a#ree!ent are
0&1 to 2&3 ,or te *
n
+ata an+ 13&1
to 6&= ,or te b
n
+ata& 7or te t%o
"ara!eters *
n
an+ b
n
2 !an-
+i,,erences are outsi+e te li!its
o, a#ree!ent2 so te results
obtaine+ b- te t%o instru!ents
are inco!"atible2 ence te nee+
to !aIe "re+iction !o+els&
?e,ore an- "re+iction
"roce+ure2 te ,irst ste" is to
e;a!ine te +ata to calculate te
!ean absolute +i,,erences
bet%een te *
n
a
n
b
n
"ara!eters o,
te re,erence instru!ent an+
tose !easure+ %it te tar#et
instru!ents& ?- co!"arin# te
colori6!eter %it te 1onica
s"ectro"oto!eter2 !ean absolute
+i,,er6ences are e/ual to
1&5 ,or *
n
2 2&1 ,or a
n
an+
4&0 ,or b
n
& .s re#ar+s te
Bunter*ab
s"ectro"oto!eter2 te
!ean absolute
+i,,erences are e/ual to
4&6 ,or *
n
2 2&2 ,or a
n
an+
4&0 ,or b
n
&
To use te
s"ectro"oto!eter
tar#et2 te "ro+ucts
assesse+ as con,or!
%it te colori!eter !ust
also be assesse+ as
con,or! i&e&2 tat te
"ara!eter values
!easure+ b- tis
s"ectro"ot6o!eter
soul+ be also %itin te
tolerance ran#e& Table 1
"resents te *
n
a
n
b
n
"ara!eters obtaine+ %it
te colori!eter an+ %it
te s"ectro"oto!eters
,or t%o con,or!e+
sa!"les& 7or so!e
"ro+ucts2 as +i,,erences
,ro! values obtaine+ b-
colori6!eter an+ b-
s"ectro"oto!eter bein#
lo%2 te ne% "ara!eters
values are still inclu+e+
in te ran#e o, toleranceN
it is te case ,or sa!"le
1& 8everteless2 ,or oter
"ro+ucts2 as sa!"le 22
assesse+ as con,or!
%it te colori!eter2
because o, te
+i,,erences in+uce+ b-
te instru!ent can#e2
te ne% values are
outsi+e te tolerance
ran#e2 ence te nee+ to
!aIe "re+iction !o+els&
L
*
1
0
5
1
5
1
6
0
1
4
0
1
0
0
a*
ta
rg
et
C
M
3
6
0
0
d
1
0
b
*
t
a
r
g
e
t
C
M
3
6
0
0
d
5
1
2
0
=
5 0
1
0
0
=
0
6
5
8
0
6
1
0
6
0
8
5
6
1
5
4
0
6
2
0
2
0
8
0
6
2
5 0
80 85 =0
=
5
10
0
10
5 620
6
1
5
6
1
0
6
5 0 5
1
0 0
2
0
4
0
6
0
8
0
1
0
0
1
2
0
1
4
0
1
6
0
L*
reference a* reference
b*
reference
7i#& 3& Scatter
+ia#ra! o, (a) *
n
2 (b)
a
n
an+ (c) b
n
,or te
C:3600+ tar#et
instru!ent ( line
o, e/ualit-2 VV
re#ression line)&
0& 1ori,i et al& ' Talanta 104 (2013) 5866 63
7i#& 4& Di,,erences +ia#ra! o, (a) *
n
an+ (b) b
n
values ,or te
C:3600+ tar#et instru!ent&
Table 1
>reli!inar- co!"arison o, te *
n
a
n
b
n
"ara!eters bet%een colori!eter an+ s"ectro"oto!eters ,or t%o con,or!
sa!"les&
>ara!eter (tolerance ran#e) Sa!"le no& 1 Sa!"le no& 2
*
n
(89'=9) a
n
(='1) b
n
(25'45) *
n
(99'89) a
n
(13'3)
b
n

(45'65)
Colori!eter =3&46 4&39 32&8= 9=&32 3&89 65&00
S"ectro"oto!eter 1onica =4&59 6&02 32&=8 96&88 2&85 91&59
S"ectro"oto!eter Bunter*ab =1&42 5&=4 32&28 94&06 2&48 6=&25
4&1& >re+ictive !o+el b- si!"le linear
re#ression
*inear re#ression !o+els ave been
calculate+ to +escribe te relationsi"
bet%een *
n
"ara!eters o, te CT310 an+ *
n
"ara6!eters o, te C:3600+2 an+ bet%een
*
n
"ara!eters o, te CT310 an+ *
n
"ara!eters o, te <ltraScan& Te sa!e
"roce+ure %as !a+e ,or te cro!aticit-
coe,,icients a
n
an+ b
n
2 as seen in 7i#& 5 &
(n te case o, te "ara!eter *
n
2 7i#& 5 (a2
b) so%s a stron# correlation an+ a lo%
relative error o, "re+iction (0)>*n R1W) b-
linear re#ression& So2 tis !o+el coul+ be
use+ to o"erate te "re+iction o, *
n
,ro! +ata
obtaine+ b- te tar#et instru!ents& Bo%ever2
7i#& 5(be) so%s tat ,or te cro!aticit-
coe,,icients a
n
an+ b
n
2 0)> are too i#
(0)>an R=0W2 0)>bn R28W)&
7i#& 2 so%s a s"ectral overla" o, te
t%o areas o, te color !atcin# ,unctions ;(l)
an+ C(l) bet%een 380 an+ 510 n!& Des"ite
tis2 tese values are use+ to calculate te
cro!aticit- coe,,icients a
n
an+ b
n
accor+in#
to te trans,er ,unctions liste+ above ()/s&
(13))& Tis s"ectral overla" coul+ e;"lain
tese si#ni,icant 0)>& Tese !o+els are not
reliable& Tere,ore2 te "re+iction !o+el
creation re/uires a !ore elaborate+
"rocessin# tan a si!"le linear re#ression&
Te ne;t lo#ical ste" is to overco!e tis
inter!e+iate ste" o, calculatin# te *
n
a
n
b
n
"ara!eters ,ro! te L3M tristi!ulus values
an+ o"erate te entire re,lectance s"ectru!&
To +o so2 te "artial least s/uares (>*S)
re#ression2 is use+& So2 it %e %ill be able to
co!"are te *
n
a
n
b
n
"ara!eters obtaine+
%it te colori!eter
an+ te re,lectance
s"ectra obtaine+
%it te tar#et
s"ectro"oto!eters
&
4&2& >re+ictive
!o+el b- "artial
least s/uares
re#ression
(n or+er to
"re+ict te sa!"les
*
n
a
n
b
n
"ara!eters
o, sa!"les2
"re+iction !o+els2
base+ on
re,lectance s"ectra2
calculate+ b- >*S
re#ression are
"er,or!e+ on eac
"ara!eter an+ ,or
eac tar#et
s"ectro!eter&
0esults are #iven in
7i#& 6& .
!ate!atical
!o+el correlates
te in"ut variables2
i&e&2 te re,lectance
values in te
s"ectral ran#e2 an+
te res"onses to
"re+ict2 i&e&2 te
*
n
a
n
b
n
"ara!eters&
Tables 2 an+ 3
#ive te ran#es2 te
nu!ber o,
ele!ents2 te
correlation
coe,,icients an+ te
errors o, te
!o+els& ?- co!"ar6
in# te results o,
te !o+els
obtaine+ ,or te t%o
s"ectro6
"oto!eters2 te
"re+iction !o+els
are /uite si!ilar but
te
s"ectro"oto!eter 1onica C:3600+ #ives a
sli#tl- better corre6lation& Tis can "robabl-
be attributable to te si!ilarit- in te sensor
s-ste! arran#e!ent e!"lo-e+ in te 1onica
:inolta colori!eter an+ 1onica :inolta
s"ectro"oto!eter& To assess te realit- o,
tese +i,,erences2 a 7iserSne+ecor test is
"er,or!e+ on te t%o S)> res"ectivel- ,or
te variables *
n
2 a
n
an+ b
n
& Tis test allo%s to
a,,ir! tat te S)> are not statisticall-
+i,,erent at a si#ni,icance level o, 5W&
Te results +e!onstrate tat te >*S
!o+els obtaine+ %it te t%o
s"ectro"oto!eters are /uite si!ilar an+
so% si#ni,icant correlations an+ #oo+
"re+ictive abilities (0
2
Z0&== an+
0&=o0)>o16)& :o+els are bot satis,actor-
,or te "re+iction2 ,ro! te tar#et
instru!ents2 o, te tree *
n
a
n
b
n
"ara!eters
o, te re,erence instru!ent& 0)>s ave been
+ivi+e+ b- 6 ,or te "re+iction o, a
n
an+ b- 2
,or te "re+iction o, b
n
co!"are+ to te
"re+iction b- linear re#ression&
To veri,- te +e"en+enc- bet%een *
n
2 a
n
an+ b
n
"ara!eters2 a re#ression test %as
"er,or!e+ b- >*S2& >*S2 re#ression is a
version o, te >*S !eto+ in %ic it is
"ossible to !o+el several variables
si!ultaneousl-2 te tree color s"ace
"ara!eters ere& Tis allo%s to assess
%eter correlations or collinearit- bet%een
variables an+ tus +eter!ine teir "ossible
+e"en+ence& Te results o, testin# b- >*S2
so% tat tis +oes not i!"rove te
"re+iction
co!"are+ to te
results obtaine+ b-
>*S1N "re+iction
errors are sli#tl-
above& Tis
in,or!ation +oes
not -et allo% to
conclu+e on te
in+e"en+ence o,
te "ara!eters o,
te color s"ace&
Oen areas o,
re,lectance s"ectra
%ic contain te
!ost in,or!ation ,or
te "ara!eter to
calculate (as so%n
on 7i#& 2 an+ in
te trans,er )/s&
(13)) are selecte+
an+ use+ to
acieve te
"re+iction !o+els
b- >*S1
re#ression2
"re+iction !o+els
are not i!"rove+&
So2 it is ,air to sa-
tat te "ara!eters
o, te *
n
a
n
b
n
color
s"ace are
in+e"en+ent
variables&
(n so!e cases2
te selection o,
in,or!ative s"ectral
re#ions ai!s to
construct better
>*S !o+els tan
tose base+ on te
overall s"ectral
ran#e& Bo%ever2 in
tis stu+-2 it +i+ not
i!"rove "re+ictive
abilit- o, >*S&
(n a++ition to te
0)> calculation2
con,or!it-
calculations %ere
carrie+ out on te
380 sa!"les
classi,ie+ as
con,or! in
accor+ance %it te
re,erence
instru!ent2 tat is
to sa- te
+eter!ination o, te
nu!ber o, sa!"les
,oun+ not con,or!
b- te tar#et
instru!ents2 an+
%oul+ tere,ore be
rejecte+ in ter!s o,
/ualit- control&
Table 4 su!!ariCes
te nu!ber o,
sa!"les
64 0& 1ori,i et al& ' Talanta 104 (2013) 5866
7i#& 5& *inear re#ression !o+els ,or *
n
(a) C:3600+2 (b) <ltraScan2 ,or a
n
(c) C:3600+2 (+) <ltraScan an+ ,or b
n
(e) C:3600+2 (,) <ltraScan&
1
0
5
1
0
0
=
5
=
0
8
5
84
8
6
8
8
=
0
=
2
=
4
=
6
=
8
1
0
0
1
0
2
5 0 65
610 615 620 625
620 618 616 614 612 610 68 66 64 62 0 2 4
1
0
0
8
0
6
0
4
0
2
0
0
0
1
0
2
0
3
0
4
0
5
0
6
0
9
0
8
0
=
0
1
0
5
1
0
0
=
5
=
0
8
5
84
8
6
8
8
=
0
=
2
=
4
=
6
=
8
1
0
0
1
0
2
5
0
6
5
6
1
0
6
1
5 :
6
2
0
620 618 616 614 612 610 68 66 64 62 0 2 4
1
0
0
8
0
6
0
4
0
2
0
0
0
1
0
2
0
3
0
4
0
5
0
6
0
9
0
8
0
=
0
7i#& 6& >*S re#ression !o+els ,or *
n
(a) C:3600+2 (b)
<ltraScan2 ,or a
n
(c) C:3600+2 (+) <ltraScan an+ ,or b
n
(e)
C:3600+2 (,) <ltraScan&
0& 1ori,i et al& ' Talanta 104 (2013) 5866
6
5
Table 2
Deter!ination o, *
n
a
n
b
n
"ara!eters b- >*S treat!ent o, re,lectance s"ectra ,ro! te 1onica C:3600+ s"ectro"oto!eter&
*
n
a
n
b
n
Calibration >re+iction Calibration >re+iction Calibration >re+iction
0an#e (W) 60102&0 202 0&01101
)le!ents 268 132 255 125 255 125
Correlation 0&==3 0&=83 0&=8= 0&=8= 0&==3 0&=8=
S)C S)> 0&95 0&86 0&69 0&93 2&94 3&14
0)>(W) (*V) 0&= (6) 15&5 (9) 14&= (9)
S)C$ stan+ar+ error o, calibration2 S)>$ stan+ar+ error o, "re+iction2 0)>$ relative error o, "re+iction2 *V$ nu!ber o, latent variables&
Table 3
Deter!ination o, *
n
a
n
b
n
"ara!eters b- >*S treat!ent o, re,lectance s"ectra ,ro! te Bunter*ab <ltraScan s"ectro"oto!eter&
*
n
a
n
b
n
Calibration >re+iction Calibration >re+iction Calibration >re+iction
0an#e (W) 60102&0 202 0&01101
)le!ents 268 132 255 125 255 125
Correlation 0&==3 0&=81 0&==0 0&=8= 0&==3 0&=89
S)C S)> 0&95 0&=1 0&69 0&96 2&64 3&46
0)>(W) (*V) 0&=(6) 16&2(9) 16&4(9)
S)C$ stan+ar+ error o, calibration2 S)>$ stan+ar+ error o, "re+iction2 0)>$ relative error o, "re+iction2 *V$ nu!ber o, latent variables&
Table 4
8u!ber o, sa!"les %ron#l- classi,ie+ as non6con,or! b- te tar#et instru!ents
>ara!eter
1onica :inolta C:63600+ Bunter*ab <ltrascan
(tolerance
ran#e)
*
n
a
n
b
n
0eject
e+
*
n
a
n
b
n
0ejecte
+
(
8
9
'
(=
'
(
2
5
'
(
9
9
'
(13
'
(
4
5
'
sa!"l
es sa!"les
=
9) 1)
4
5
)
8
9
) 3)
6
5
)
8on con,or!
be,ore
2
6
3
=
5
2
8
8
3
3
8
4
9
4
=
34
9
treat!ent
8on con,or!
a,ter linear 0
1
8
2
8
3
0 1
2
0
2
9 33
re#ression
8on con,or!
a,ter >*S 0 6 9 8 1 6 9 10
re#ression
%ron#l- classi,ie+ as non6con,or! b- te tar#et instru!ents be,ore
an+ a,ter treat!ent o, te "ara!eter values *
n
a
n
b
n
b- linear
re#ression an+ b- >*S& . sa!"le avin# a value out o, ran#e ,or at
least one o, te tree
"ara!eters %as rejecte+& Oit
te 1onica :inolta C:3600+
instru!ent2 9W o, te sa!"les
%ere rejecte+ accor+in# to
teir out o, ran#e *
n
value2
10W ,or a
n
an+ 14W ,or b
n
&
Te nu!ber o, rejecte+
sa!"les reaces 23W& So!e
sa!"les %ere +e,ective
accor+in# to several
"ara!eters2 tat is %- te
,inal nu!ber o, rejecte+
sa!"les %as less tan te
su! o, te nu!ber o, rejecte+
sa!"les accor+in# to one o,
te tree "ara!eters& .n
avera#e o, 38W o, te
sa!"les %as rejecte+ %it te
Bunterlab <ltraScan
instru!ent +ue to a ver- "oor
concor6+ance o, tis
instru!ent %it te re,erence
instru!ent ,or te *
n
values&
Te linear re#ression
treat!ents #reatl- re+uce te
nu!ber o, sa!"les
!isclassi,ie+& Oit te 1onica
:inolta C:3600+ instru!ent2
neiter sa!"le %as
+eclassi,ie+ an+ %it te
Bunterlab <ltraScan
instru!ent onl- one sa!"le
%as +eclas6si,ie+ because o,
its %ron# *
n
value& Oit bot
instru!ents2 tere %ere onl-
6W an+ 9W2 res"ectivel- o, te
a
n
an+ b
n
values tat %ere
,oun+ out o, ran#es& 7inall-2
8W o, te sa!"les %ere
rejecte+ %it te 1onica
:inolta C:3600+ instru!ent
an+ =W %it te Bunterlab
<ltraScan instru!ent& >*S
re#ression +i+ not i!"rove
Table 5
8u!ber o, sa!"les %ron#l- classi,ie+ as non6con,or! ,or at least one "ara!eter
non con,or! b- te tar#et instru!ents&
>ara!eter (tolerance ran#e) 1onica :inolta C:6 Bunter*ab
3600+ <ltrascan
*
n
a
n
b
n
*
n
a
n
b
n
8on con,or! be,ore treat!ent
8
8
34
9
8on con,or! a,ter linear
3
0 33
re#ression
8on con,or! a,ter >*S
8 10
re#ression
te *
n
results but te nu!ber o, rejecte+ sa!"les %ere re+uce to
2W %it te values "re+icte+ b- te >*S re#ression Table& 5 &
>*S re#ression is a !ore e,,ective tecni/ue tat can acieve
better /ualit- !o+els tan tose obtaine+ b- linear re#ression&
(n+ee+2 te 0)> an+ te correlation coe,,icients in+icate te
"re+ictive /ualit- o, te correlation !o+els2 %ic are not ba+ ,or a
routine a""lication& 7inall-2 te best "re+iction !o+els obtaine+ are
tose !a+e in+e"en+entl- ,or
te tree "ara!eters on te
%ole re,lectance s"ectra b-
>*S1 re#ression&
5& Conclusion
Te ai! o, te stu+- %as to
be able to "re+ict ,ro! te
!easure+ values o, te tar#et
instru!ents2 te values tat
%oul+ ave resulte+ on te
re,erence instru!ent %it an
error as s!all as "ossible2 te
,inal outco!e is to enable te
/ualit- control laborator- to
!aintain its current control
!a"s& To be +one2 it %as
necessar- to "rovi+e te best
"re+iction !o+el bet%een te
re,erence instru!ent2 a
tristi!ulus colori!eter an+ te
tar#et ones2 t%o benc6to"
s"ere s"ectro"oto!eters&
An te basis o, te results
acieve+ in tis %orI2
"re+ictive !o+els o, te
C()*
n
a
n
b
n
color s"ace are
,easible ,or te t%o
s"ectro"oto!etr- +evices&
Te various ce!o!etric tools
teste+ so% tat te >*S1
re#ression a""lie+ on te
entire re,lectance s"ectra o,
eac "ara!eter o, te color
s"ace is te one tat acieves
te best "re+iction !o+els&
Tese !o+els can res"on+
"ositivel- to te issue o,
re"lace!ent o, laborator-
e/ui"!ent&
66 0& 1ori,i et al& ' Talanta 104 (2013) 5866
0e,erences
[1] D.B. MacDougall, Colou !n "oo#$ %m&ov!ng 'ual!t(,
Woo#hea# Pu)l!*h!ng, +,,+.
[2] -... Roth, /. Ra#le, 0.R. 1!22o#, ".M. Cl(#e*#ale, 3. "oo#
0c!. 45 (6788) 66669666+.
[3] C. Calvo, .. 0alva#o, 0.M. "!*zman, :u. "oo# Re*. ;echnol.
+65 (+,,6) 7796,5.
[4] ..3. Mele<n#ez=Mat><nez, %.M. ?!ca!o, ".3. -ee#!a, "oo#
'ual. Pe2eence 66 (+,,4) @A69@A8.
[5] ?./.P. "ee!a, 0.?. "enan#e*, B. Cot*u(anag!, Rev. :*&.
C!enc. ;echnol. .l!ment. 5@ (677@) 56695++.
[6] D. .n*oena, M.P. De PenDa, %. .*t!a*aa<n, 3. Bello, 3. Meat
0c!. @6 (677A) 5659568.
[7] ..3. Mele<n#ez=Mat><nez, %.M. ?!ca!o, ".3. -ee#!a, 3. .g!c.
"oo# Chem. 46 (+,,5) A+669A+A,.
[8] /. Du2o**e<, P. 1alau&, :. Calet, C. "lam!n, .. ?alla, "oo#
Re*. %nt. 58 (+,,4) 76797+@.
[9] M.3. Mo(ano, ..3. Mele<n#ez=Mat><nez, 3. .l)a, ".3. -ee#!a,
"oo# Re*. %nt. @6 (+,,8) 46594+6.
[10] ?.1. Mata, P.B. 1ome*, ..:. Ro#!gue*, %n#. :ng. Chem. Re*.
46 (+,,4) +85@9+84+.
[11] 3.C. EF!nGel*, D!*&la(* 66 (6776) 66596A6.
[12] B.0. Bu*l!g, Poc. "la. 0tate. -ot. 0oc. 6,@ (6776)
656965@.
[13] .. "ulleton, 3. Be!#!ng, 0G!n Re*. ;echnol. 5
(677A) +5A9+@6.
[14] ..3. Mele<n#ezMat><nez, %.M. ?!ca!o, ".3.
-ee#!a, 3. 0c!. "oo# .g!c. 84 (+,,4) 87@97,6.
[15] 1. W(*zecG!, W.0. 0t!le*, Colo 0c!ence$ Conce&t*
an# Metho#*, 'uant!tat!ve Data an# "omulae, *econ# e#.,
W!le(=%nte*c!ence, +,,,.
[16] C%:, C%: 67A6 /
n
a
n
)
n
Colo 0&ace, %0H 6666@=@$+,,8(:)IC%:
0 ,6@=@I: (+,,A).
[17] C%:, C%: ;!*t!mulu* ?alue*, C%: 0 ,6@=5I: (+,66).
[18] B.M.M. B!*hna Pa*a#, 0. Raheem, P.
?!Ja(aleG*hm!, C.Bamala 0a*t!, ;alanta @5 (6776)
668A96+,6.
[19] D. %*aac* Metho# an# .&&aatu* 2o Colo
0&ecto&hotomet(, Patent num)e 58A@A77 (67A4).
[20] C%:, C%: 0tan#a# %llum!nant* 2o
Colo!met(, %0H 6666@=+$+,,A(:)IC%: 0 ,6@=+I:
(+,,6).
[21] C%:, C%: 0tan#a# Colo!met!c H)*eve*,
%0H 6666@=6$+,,A(:)IC%: 0 ,6@=6I: (+,,A).
[22] 0. Wol#, -. Maten*, -. Wol#, ;he
mult!va!ate cal!)at!on &o)lem !n chem!*t(
*olve# )( the P/0 metho#, Mat!K Penc!l*, 0&!nge
Bel!n -e!#el)eg, &&. +869+75.
[23] 3.M. Blan#, D.1. .ltman, /ancet (6786) 5,A956,.