Ac a Geodyn. Geoma e ., Vol. 8, No. 1 (161), 59–67, 2011
CHARACTERIZATION AND DIFFERENTIATION OF KAOLINITES FROM
SELECTED CZECH DEPOSITS USING INFRARED SPECTROSCOPY
AND DIFFERENTIAL THERMAL ANALYSIS
.
Lenka VACULÍKOVÁ 1), E a PLEVOVÁ 1)*, Sil ie VALLOVÁ 2) and I an KOUTNÍK 2)
1) Ins i u e o Geonics, Academy o Sciences o he Czech Republic, . .i., S uden ská 1768, 708 00 Os a a,
Czech Republic
2) Technical Uni e si y o Os a a, 17. lis opadu 15, 708 33 Os a a, Czech Republic
*Co esponding au ho ‘s e-mail: ple o [email protected]
(Recei ed Sep embe 2010, accep ed Decembe 2010)
ABSTRACT
This pape epo s he possibili ies o using FTIR spec oscopy and simul aneous he mog a ime y and di e en ial he mal
analysis o examina ion o he s uc u al o de o ou Czech kaolini e samples (Jimliko , Sedlec, Olomucany and Unano
deposi s) and one kaolini e s anda d KGa-1b om Geo gia deposi ob ained om he Sou ce Clays Reposi o y o The Clay
Mine als Socie y (USA). FTIR spec oscopy was used o he classi ica ion o he deg ee o s uc u al o de o kaolini e
samples by empi ical (IR-E) and nume ical (IR-N) classi ica ion. Di e en ial he mal analysis was used o he de e mina io
n
o he kaolini e diso de deg ee acco ding o decomposi ion peak empe a u e ob ained om DTA cu es. The esul ing
end o dec ease in o de liness is: KGA-1b (wi h he bes o de liness) > Jimliko > Sedlec > Olomucany > Unano (wi h he
wo s o de liness).
KEYWORDS: kaolini e, deg ee o s uc u al o de , in a ed spec oscopy, he mog a ime y and di e en ial he mal analysis
a hickness o app oxima ely 7 Å. The poo s uc u al
o de commonly obse ed in kaolini es can be
explained in e ms o a se ies o s acking aul s o
de ec s in he ab plane and along he c-axis. The XRD
p
a e ns o o de ed kaolini e samples a e signi ican ly
di e en om hose o diso de . O de ed kaolini e
shows sha p and na ow peaks, while i s diso de ed
coun e pa gi es less well-de ined, b oad, and
asymme ical peaks (B iga i e al., 2006). The
c ys allini y indices gi en by many au ho s a e widely
used o de e mina ion o kaolini e diso de deg ee
using a ious app oaches based on X- ay di ac ion
(B indley e al., 1963; Plancon and Zacha ie, 1990;
Apa icio and Galán, 1999; Chmielo á and Weiss,
2002; Apa icio, 2006).
Less common used me hod o de e mina ion o
kaolini e diso de deg ee is an in a ed spec oscopy.
The s uc u al diso de o kaolini es can be de ec ed
b
y di e ences in posi ion and ela i e in ensi y o OH
s e ching and bending bands in IR spec u
m
(B indley, e al., 1986; Mulle and Bocquie , 1987;
P os e al., 1989; Madejo á e al., 1997). On he basis
o change in he ela i e in ensi ies o abso p ion
b
ands co esponding o he s e ching and bending
ib a ions o s uc u al OH g oups, i was possible o
di ide he analyzed samples in o h ee g oups: wi h
o de ed s uc u e, pa ially o de ed s uc u e an
d
poo ly o de ed s uc u e.
1. INTRODUCTION
Impo an deposi s o high quali y kaolin in he
Czech epublic (sedimen a y ock, wi h a signi ican
p opo ion o kaolini e and o he clay mine als) a e in
Ka lo y Va y egion. A mo e ex ensi e deposi s o
kaolin a e in he egion o Ho ni B iza, Kaznejo ,
Cho iko and o he places in he no he n
neighbo hood o Pilsen. Low-quali y kaolin deposi s
a e si ua ed in wes e n Bohemia and also in Znojmo
dis ic . Kaolin is widely used in he pape indus y o
i s high whi eness and low ab asion and i is also use
d
in he o he indus y b anches like cons uc ion,
ce amics, ubbe and po celain manu ac u ing.
The empi ical o mula o kaolini e is
Al2Si2O5(OH)4 and he heo e ical chemical
composi ion is SiO2, 46.54 %; Al2O3, 39.50 %; and
H2O, 13.96 %. Kaolini e has a 1:1 shee s uc u e
consis ed by e ahed al and oc ahed al shee s. Type
1:1 mine als gene ally do no ha e he cha ge o i s
alue is ex emely low (Mu ay, 2007). The kaolini e
laye ed s uc u e 1:1 acco ding o (Kühn an
d
Zama ský, 1984) is shown in Figu e 1.
The quali y espec i ely he o de liness o
kaolini es s ongly in luence hei physical an
d
chemical p ope ies. The mos o en used me ho
d
o examina ion o he deg ee o s uc u al
diso de o “c ys allini y” o he kaolini e samples
is X- ay powde di ac ion. Kaolini e e ahed al
and oc ahed al ne wo k o ms a single laye wi h
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
L. Vaculíko á e al.
60
Fig. 1 The kaolini e laye ed s uc u e 1:1.
modes ob ained by FTIR measu emen s as well as he
de e mina ion o he diso de deg ee acco ding o pea
k
empe a u e alues o kaolini e dehyd oxila ion an
d
ans o ma ion ob ained by di e en ial he mal
analysis.
2. SAMPLES AND EXPERIMENTAL METHODS
2.1. TESTED SAMPLES
Kaolini e samples ( ac ion unde 5μm) o
m
se e al di e en Czech kaolin deposi we e used o
analysis:
(a) kaolini e sample om Ka lo y Va y egion,
o med by kaoliniza ion o g ani e (Jimliko u
Chodo a locali y)
(b) kaolini e sample om Ka lo y Va y egion,
o med by kaoliniza ion o g ani e (Sedlec
locali y)
(c) kaolini e sample om Mo a ian Ka s ,
ep esen ed kaolinized clayey-sandy sedimen s in
osil-ka s dep essions (Olomucany locali y)
(d) kaolini e sample om Znojmo egion, o med by
kaoliniza ion o g ani oid ocks (Unano locali y)
(e) kaolini e sample KGa-1b om Geo gia (USA),
ep esen ed sedimen a y kaolini e wi h well
o de ed s uc u e.
Following Table 1 shows he olume o kaolini e
and ype o associa ed mine als signed as : Q - qua z,
I – illi e, Sm – smec i e, D – dicki e, F – eldspa .
The leas common used me hod o
de e mina ion o kaolini e diso de deg ee is
simul aneous he mog a ime y and di e en ial
he mal analysis. The DTA cu es show he
endo he mic and exo he mic eac ions in a kaolini e
sample du ing hea ing, such as deso p ion o su ace
wa e (H2O), dehyd oxila ion (s uc u al OH- g oups)
and he ans o ma ion o mulli e and c is obali e
(Főld á i, 1997; Ha akeyama and Liu, 1998;
Guggenheim and Kos e an G oos, 2001). The
ob ained empe a u e e ec s o dehyd oxila ion and
p
olymo phic ans o ma ion a e s ongly dependen on
kaolini e sample s uc u al o de (Smyka z-Kloss,
1974; K is ó e al., 2002).
In he p esen pape is inco po a ed a de ailed
s udy o he deg ee o s uc u al diso de o ou
Czech kaolini e samples (Jimliko , Sedlec,
Olomucany and Unano deposi s) and one kaolini e
s anda d KGa-1b om Geo gia deposi ob ained o
m
he Sou ce Clays Reposi o y o The Clay Mine als
Socie y (USA). The kaolini e s anda d KGa-1b is he
aim o he in e es o many au ho s because o i s
p
u i y and i s special p ope ies (P ue and Webb,
1993; Be ezni ski e al., 1998; Sanchez-So o e al.,
2000; Me mu and Cano, 2001; T ao é, 2006). This
s anda d kaolini e was chosen o compa ision wi h
Czech selec ed kaolini es men ioned abo e. The
de ailed s udy has included mainly an nume ical
app oach based on c ys allini y indices CI1 and CI2
calcula ed om he in ensi ies o selec ed ib a ions
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
CHARACTERIZATION AND DIFFERENTIATION OF KAOLINITES FROM …
.
61
Table 1 Locali y, mine alogical composi ion, genesis and classi ica ion acco ding o XRD o es ed kaolini e
samples.
XRD
Deposi Kaolini e
(%)
Associa ed
mine als
O igin HI AGFI Class.
Geo gia (KGa-1b), USA 96 D sedimen a y 1.120 - w-o
Jimliko u Chodo a, CZ 98 Q wea he ed 1.060 1.180 o
Sedlec u K. Va u,CZ 97 Q,I,Sm wea he ed 0.630 0.780 p-o
Olomucany,Blansko, CZ 97 Q,I,Sm wea he ed 0.590 0.670 p-o
Unano u Znojma, CZ 96 Q,I,F wea he ed 0.480 0.640 p-o
HI - he me hod o Hinckley (1963)
AGFI - he me hod o Apa icio-Galán_Fe ell (1999)
classi ied as poo ly o de ed s uc u es (CI1 < 0.7,
CI2 > 1.2); pa ially o de ed s uc u es (0.7 < CI1
< 0.8, 0.9 < CI2 < 1.2) and o de ed s uc u es
(CI1 > 0.8, CI2 < 0.9) (Russell and F ase , 1994;
Madejo á and Komadel, 2001).
2.3. METHOD OF THERMAL ANALYSIS
Simula neous he mog a ime y and
di e en ial he mal analysis was ca ied ou using
mul imodula he mal analyze SETSYS 12 -
SETARAM ins umen equipped wi h a measu emen
head TG ATD ROD acco ding o below men ioned
condi ions. Measu emen o each sample was ca ied
i e imes o ge p edica i e esul s.
Based on ob ained DTA cu es, espec i ely
acco ding o decomposi ion peak empe a u es is
p
ossible o de e mine he deg ee o diso de in
kaolini e samples. Well o de ed sample has hei
decomposi ion peak empe a u e o qui e high alue
(Td > 571 °C), o de ed sample has hei decomposi ion
peak empe a u e Td a he empe a u e in e al 561-
570 °C. Fo poo ly o de ed sample, he empe a u e
decomposi ion a ies om 546 o 560 °C and
diso de ed sample decomposi ion empe a u e
alues is up o 545 °C. The decomposi ion peak below
540 °C seems o be qui e low acco ding o publishe
d
DTA da a o kaolini es and belog o only a e y ew
na u ally occu ing, ex emely diso de ed samples.
The di e en ia ion men ioned abo e can be used
o he de e mina ion o he diso de deg ee o
kaolini es i he analysis we e unde he p oposed
condi ions : hea ing a e 10 °C.min-1, sample ac ion
unde 5 μm ( he ac ion om 0.5 o 5 μm wi h
maximum in hei g ain size dis ibu ion cu es laying
o he ac ion 2 – 3 μm) , sample mass abou 50 mg,
he mocouple P -P 90/Rh10, ine ma e ial Al2O3, no
p essing in c ucible (loose packed), ai a mosphe e.
Wi h di e en condi ions, he dehyd oxila ion pea
k
empe a u e Td can a y, so he empe a u e in e al o
diso de deg ee can di e oo. The mos in luencing
ac o o he Td empe a u e alue is he hea ing a e
2.2. METHOD OF FTIR SPECTROSCOPY
The in a ed spec a we e eco ded on Nicole
A a a 320 FTIR spec ome e . The KB p essed-disc
echnique was used o ou ine scanning o he
spec a. Samples o 2 mg and 0.5 mg we e dispe se
d
in 200 mg o KB o eco d op imal spec a in
he egions o 4000-3000 and 4000-400 cm-1 wi h
a esolu ion o 4 cm-1 and 64 scans. Discs o he
4000-3000 cm-1 egion we e hea ed in he u nace
o e nigh a 150 °C o minimize he wa e adso be
d
on KB and clay sample (Madejo á e al., 1997).
Two app oaches we e used o de e mine he
deg ee o s uc u al diso de o selec ed kaolini es
om IR spec a. The i s ly s ep, an empi ical
app oach (IR-E) on he basis o esolu ion and ela i e
in ensi ies o he bands in OH s e ching and bending
egion was used. The samples we e classi ied as:
• o de ed (well - o de ed) i he OH s e ching and
bending bands we e clea ly esol ed;
• pa ially o de ed i he indi idual OH bands a
3670, 3650 and 938 cm-1 could be iden i ied bu
hei in ensi ies we e low; and
• poo ly o de ed i only one band nea 3660 o
in lexions nea 3670, 3650 and 938 cm-1 we e
obse ed in he spec a (Madejo á e al., 1997).
A nume ical app oach (IR-
N
) based on
c ys allini y indices CI1 and CI2 calcula ed om he
in ensi ies o selec ed ib a ions modes using he
equa ions:
CI1 = I(ν1) / I(ν3) (1)
CI2 = I(ν4) / I(ν1) (2)
whe e I(ν1) and I(ν4) a e in ensi ies o he OH
s e ching bands a 3695 cm-1 and 3620 cm-1 and I(ν3)
is he in ensi y o he OH bending band a 915 cm-1.
The wo-
p
oin s baseline me hod was used o ob ained
he in ensi y o he OH bands. Acco ding o he
ob ained alues o c ys allini y indices kaolini es we e
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
L. Vaculíko á e al.
62
3. RESULTS AND DISCUSSION
3.1. FTIR SPECTROSCOPY
The in a ed spec a o es ed kaolini es a e
shown in Figu es 2 and 3. The comple e assignmen o
he abso p ion bands in measu ed IR spec a is
summa ized in Table 2.
De e mina ion o deg ee o s uc u al diso de
om IR spec a o kaolini es based on isual
es ima ion o speci ic ea u es (IR-E) and calcula ed
(Gabbo , 2008). The di e ence be ween he
dehyd oxila ion empe a u e wi h hea ing a es
3 °C.min-1 and 30 °C.min-1 o he same kaolini e
sample is o e 50 °C. The e o e he e alua ion o he
diso de deg ee o kaolini es by he mal analysis mus
be always adjus ed o measu emen condi ions
(Smyka z-Kloss, 1974).
Table 2 Possi ion and assignmen o he abso p ion bands in IR spec a o es ed kaolini es.
Assignmen KGa-1b Jimliko Sedlec Olomucany Unano
OH s e ching o inne -su ace
hyd oxyl g oups1 3694 3695 3696 3696 3696
OH s e ching o inne -su ace
hyd oxyl g oups2 3669 3669 3668 3668(s) 3669
OH s e ching o inne -su ace
hyd oxyl g oups2 3653 3652 3653 3654 3652
OH s e ching o inne
hyd oxyl g oups 3618 3620 3620 3620 3620
Si-O s e ching
(longi udinal mode) 1113(s) 1112 1113 1111 1114
Si-O s e ching
(pe pendicula mode) 1098 - - - -
in-plane Si-O s e ching 1033 1032 1032 1032 1032
in-plane Si-O s e ching 1009 1008 1007 1006 1007
OH de o ma ion o inne -
su ace hyd oxyl g oups 937 935 937 936 935
OH de o ma ion o inne
hyd oxyl g oups 913 913 913 913 912
Si-O 791 793 793 793 794
Si-O, pe pendicula 752 755 755 755 754
Si-O, pe pendicula 694 699 699 698 697
Si-O 645 647 641 645 644
Al-O-Si de o ma ion 540 538 537 538 537
Si-O-Si de o ma ion 468 470 469 470 469
Si-O de o ma ion 433 430 430 430 429
1 - in plane ib a ion wi h a ansi ion momen nea ly pe pendicula o he (001) plane
2 - an i-phase ib a ion wi h a ansi ion momen lying in he (001) plane.
(s) - shoulde o abso p ion band
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
CHARACTERIZATION AND DIFFERENTIATION OF KAOLINITES FROM …
.
63
Fig. 2 The in a ed spec a o kaolini es (400 o 1200 cm-1).
Fig. 3 The in a ed spec a o kaolini es (3560 o 3750 cm-1).
KGa-1b, Jimliko , Sedlec and Unano . The I
R
spec um o kaolini e om Olomucany deposi
showed he eplacemen o he middle wo bands by
a single b oad band a 3654 cm-1 wi h a shoulde nea
3668 cm-1, ha indica es pa ially o de ed s uc u e o
his sample (Fig. 3). IR spec um o Unano
demons a ed gene al b oadening o all bands (Fig. 2).
This ea u e con i ms high deg ee o diso de ing in
c ys allini y indices CI1 and CI2 (IR-
N
) acco ding o
N
eal and Wo al (1977) a e gi en in Table 3.
The 3695, 3620 cm-1 double is cha ac e is ic o
he kaolin g oup gene al. Fou clea ly esol e
d
abso p ion bands a abou 3695, 3670, 3650 and
3620 cm-1 e lec high s uc u al o de ing o he
samples. Dis inguishable ou bands in OH s e ching
egion we e obse ed in IR spec um o sample
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012

L. Vaculíko á e al.
64
Table 3 Classi ica ion o he deg ee o s uc u al o de o kaolini e samples using empi ical (IR-E) and
nume ical (IR-N) classi ica ion.
A ibu es IR-E IR-N
Deposi
1s 2
nd 3
d 4
h class
CI1 CI2
class
Geo gia (KGa-1b), USA     o 0.96 0.78 o
Jimliko u Chodo a, CZ     o 0.93 0.78 o
Sedlec u Ka lo ych Va u, CZ   937 (s)  pa-o 0.91 1.20 pa-o
Olomucany, Blansko, CZ   937 (s)  p-o 0.74 0.82 pa-o
Unano u Znojma, CZ   937 (s)  p-o 0.72 0.81 pa-o
A ibu es: 1s - dis inguishable ou bands 3695, 3670, 3650, 3620
2
nd – gene al b oadening o all bands is no obse ed
3
d - OH de o ma ion bands 938 and 916 a e isible
4
h – wo weak bands ound a 795 and 758 a e o abou equal in ensi y
CI1, CI2 – he me hod o Neal and Wo al (1977)
abso p ion a 3695 cm-1. The p oblem is ha hei
con ibu ion o he abso p ion a 915 cm-1 is
signi ican ly highe han o he abso p ion a
3695 cm-1. When calcula ing he a io o CI2
b
ased on
such a ec ed alues, he a io can indica e an
e oneously highe alue o he c ys allini y deg ee o
he kaolini e.
3.2. THERMAL ANALYSIS
The measu ed DTA cu es o es ed kaolini es
showed he ollowing endo he mic e ec s: deso p ion
o su ace wa e a low empe a u e in e al 105-
110 °C and eleasing o cons i u ion wa e an
d
b
eaking o c ys al la ice a highe empe a u e
in e al 552-576 °C. The ec ys alliza ion and ans-
o ma ion o dehyd a ed subs ance o mulli e,
c is obali e and qua z was obse ed as he exo he mic
e ec a abou 982-1001 °C.
Table 4 shows he he mal da a ob ained o
m
DTA cu es including dehyd oxila ion pea
k
empe a u e Tdand ans o ma ion peak empe a u e
T . The i s g oup o well o de ed samples is
ep esen ed by kaolini e KGa-1b wi h he highes
decomposi ion peak empe a u e alue (abo e
571 °C). The sample classi ied as o de ed ( o
m
Jimliko ) belongs o he second g oup wi h middle
decomposi ion peak empe a u e alues. Among
poo ly-o de ed samples in he hi d g oup belong
kaolini e samples om Sedlec, Olomucany and
Unano wi h he lowes decomposi ion pea
k
empe a u e alues up o 560 °C.
F om ob ained da a is e iden , ha wi h
inc easing o decomposi ion peak empe a u e alue,
espec i ely wi h inc easing o o de liness, he
ans o ma ion exo he mic peak empe a u e also
inc ease (Fig. 4). DTA cu es show, ha o well
o de ed samples, he ans o ma ion exo he mic peaks
kaolini e. Two clea ly esol ed OH bending bands
occu ing a abou 938 and 916 cm-1 we e obse ed in
IR spec a o samples om Geo gia (KGa-1b) and
Jimliko deposi (Fig. 2). O he samples in his
spec al egion showed only a e y weak in lec ion
loca ed a 934 cm-1. In all IR spec a we e ound wo
weak bands a 795 and 758 cm-1 wi h abou equal
in ensi y (Fig. 2). This a ibu e can help o dis inguish
be ween well-c ys allized kaolini e and halloysi e.
I is possible o di ide es ed kaolini es acco ding
o isual es ima ion o deg ee o c ys allini y om I
R
spec a (IR-E) in o h ee g oups: o de ed (well
o de ed), pa ially o de ed and poo ly o de ed. Fi s
g oup is ep esen ed by kaolini e KGa-1b and
Jimliko whose IR spec a sa is y all he demands o
IR-E classi ica ion. IR spec um o Sedlec kaolini e
wi hou clea ly esol ed OH de o ma ion band a
938 cm-1 belongs o he second g oup wi h pa ial
s uc u al o de . Kaolini e Olomucany and Unano
ep esen hi d g oup wi h poo ly o de s uc u e.
Acco ding o calcula ed alues o IR-N classi ica ion,
based on he a io hyd oxyl band abso bances 3695
and 915 cm-1 (CI1); and 3695 cm-1 (CI2), i is posible
o di ide he kaolini es in o wo g oups: o de ed (well
o de ed) and pa ially o de ed. Among o de ed (well
o de ed) kaolini es belong KGa-1b and Jimliko . In
his case da a om IR-E classi ica ion co espond well
wi h IR-N classi ica ion. Second g oup is ep esen e
d
by kaolini e Sedlec, Olomucany and Unano , whose
CI1 and CI2 c ys allini y indices co esponded o
pa ially o de ed s uc u es. Disc epancy be ween IR-
N
and IR-E classi ica ion a ose p obably hank o
admix u e o ine-g ained illi e o smec i e p esen in
kaolini e samples (see Table 1). Bo h mine als (illi e
and smec i e) ha e hei abso p ion bands a he same
a ea and can con ibu e o he inc easing o bo h OH
bending abso p ion a 915 cm-1 and OH s e ching
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
CHARACTERIZATION AND DIFFERENTIATION OF KAOLINITES FROM …
.
65
Table 4 The mal da a including dehyd oxila ion peak empe a u e Td , ans o ma ion peak empe a u e T and
classi ica ion o diso de deg ee o kaolini e samples.
Deposi Td T class
Geo gia (KGa-1b), USA 576 1001 w-o
Jimliko u Chodo a, CZ 570 992 o
Sedlec u Ka lo ych Va u,CZ 560 989 p-o
Olomucany,Blansko, CZ 558 988 p-o
Unano u Znojma, CZ 552 982 p-o
Fig. 4 DTA cu es o kaolini e samples Geo gia (KGa-1b) and Unano .
es ed kaolini e samples a he hea ing a e
10 °C.min-1. Wi h inc ease o peak empe a u e on
DTG cu e, ac i a ion ene gy o dehyd oxila ion
p ocess dec eased. The alues o ac i a ion ene gy Ea
a ied om 230 kJ.mol-1 (well o de ed kaolini e
sample KGa-1b) o 301 kJ.mol-1 ( he poo lies o de e
d
sample Unano ) wi h he eac ion o de n a ied o
m
0.9 o 1.5. Ob ained esul s show, ha be e o de ed
samples display lowe ac i a ion ene gy o
dehyd oxila ion p ocess es ima ed by F eeman-Ca oll
me hod. The possibili ies and compa ision o
F eeman-Ca oll me hod wi h o he used me hods a e
desc ibed well by (Slo ak, 2001). The disad an age o
his me hod can lay in he ac , ha he calcula ion is
p
e o med om he di e ence o wo disc e e
expe imen al poin s and conside a he homogenous
cha ac e o eac ion. MacKenzie (1978) and Cicel e
al. (1981) assume, ha homogeneous and
inhomogeneous mechanisms o he dehyd oxila ion
a e o he high in ensi y and qui e na ow. Fo he
poo ly o de ed sample, he ans o ma ion peaks a e
o low in esi y, wide and smalle .
The kine ic pa ame e s o decomposi ion was
s udied using he A henius equa ion applied o solid
s a e eac ions. The ac i a ion ene gy o
dehyd oxila ion was e alua ed by F eeman-Ca oll
me hod which enables, om he exploi a ion o one
DTG peak, o de e mine besides ac i a ion ene gy o
eac ion also he eac ion o de and he a e cons an
(F eeman and Ca oll, 1958). Table 5 summa ized
he mal da a including maximal eac ion eloci y
empe a u e T , ac i a ion ene gy Eawi h o de
eac ion n and co ela ion ac o R2.
I is e iden , ha alues o maximal eac ion
eloci y empe a u e T ob ained om DTG cu e
co espond o he decomposi ion peak empe a u e T
d
ob ained om DTA cu es. Figu e 5 shows he
de i a i e he mog a ime ic (DTG) cu es o all
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
L. Vaculíko á e al.
66
Table 5 The mal da a including peak empe a u e T , ac i a ion ene gy Ea and eac ion o de n.
Deposi T
°C
Ea
kJ.mol-1 n R2
Geo gia (KGa-1b). USA 573 230 1.1 1.0000
Jimliko u Chodo a. CZ 568 242 1.4 0.9998
Sedlec u Ka lo ych Va u.CZ 563 277 1.5 0.9998
Olomucany.Blansko. CZ 559 274 1.0 0.9992
Unano u Znojma. CZ 553 301 0.9 0.9996
Fig. 5 DTG cu es o kaolini e samples.
Jimliko , he second g oup o low-deg ee o s uc u al
o de (poo ly o de ed) samples con ains kaolini es
om Sedlec, Olomucany and Unano deposi s.
Acco ding o ou DTA esul s, kaolini e Geo gi
a
(KGa-1b) belongs o well-o de ed g oup, kaolini e
Jimliko o o de ed g oup and o he es ed samples o
poo ly-o de ed g oup. I is e iden , ha DTA da a se
a easonable ag eemen wi h published da a ob aine
d
b
y XRD di ac ion me hod. In case o using FTI
R
spec oscopy, he e is only a sligh di e ence be ween
IR da a and da a e alua ed by DTA and XRD
analysis. The OH s e ching and bending ib a ions o
s uc u al wa e a e sensi i e enough o dis inguish
o de ed (well o de ed), pa ially o de ed and poo ly
o de ed kaolini es. Visual IR-E me hod o s uc u al
o de de e mina ion p o ides basic classi ica ion in o
h ee g oups: o de ed (well o de ed), pa ially o de e
d
and poo ly o de ed; while IR-
N
me hod di ides
p ocess is possible. The e o e i he he e ogenous
cha ac e o dehyd axila ion p ocess is supposed, he
dependance o ac i a ion ene gy on s uc u al o de
can di e , mainly i we coside ha he
dehyd oxila ion p ocess is ini ia ed in he de ec
places.
4. CONCLUSIONS
The ob ained esul s om in a ed spec oscop
y
and di e en ial he mal analysis we e compa ed wi h
XRD esul s
p
e iously published by Hinckley (1963)
and Apa icio e al. (1999). Also acco ding o P ue
and Webb (1993), kaolini e Geo gia (KGa-1b) is
signed as well-o de ed and based on he calcula ed
cha ac e is ic (Chmielo á and Weiss, 2002), he
kaolini es om Czech deposi s can be di ided in o
wo g oups. Fi s g oup o medium-deg ee o
s uc u al o de (o de ed) samples con ains kaolini e
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012
CHARACTERIZATION AND DIFFERENTIATION OF KAOLINITES FROM …
.
67
Analysis. John Wiley & Sons L d., London.
Hinckley, D.N.: 1963, Va iabili y in “c ys allini y” alues
among he kaolin deposi s o he coas al plain o
Geo gia and Sou h Ca olina. Clays and Clay Mine als,
II, 229–235.
K is ó , J. e al.: 2002, De ec ion o ou di e en OH-
g oups in g ound kaolini e wi h con olled- a e
he mal analysis. J. The m. Anal. Calo im., 69, 77–83.
Kühn, P. and Zama ský, V.: 1984, Sys ema ic mine alogy II
– silica es, VŠB Os a a, (in Czech).
Madejo á, J. and Komadel, P.: 2001, Baseline s udies o he
clay mine als sou ce socie y: in a ed me hods. Clays
Clay Mine ., 49, 410–432.
Madejo á, J., K aus, I., Tunega, D. and Šamajo á, E.: 1997,
Fou ie ans o m in a ed spec oscopic
cha ac e iza ion o kaolin g oup mine als om he
main Slo ak deposi s. Geologica Ca pha ica – Se ies
Clays, 6, 1, 3–10.
MacKenzie, K.J.: 1978, Fea s o clay, o mine al chemis y
e isi ed. Chemis y in New Zealand, N3, 8–12.
Me mu , A.R. and Cano, A.F.: 2001, Baseline s udies o he
clay mine als socie y sou ce clays: chemical analysis
o majo elemen s. Clays Clay Mine ., 49, 381-386.
Mulle , J.P. and Bocquie , G.: 1987, Dissolu ion o
kaolini es and accumula ion o i on oxides in la e i ic-
e uginous modules: Mine alogical an
d
mic os uc u al ans o ma ions. Geode ma, 37, 113–
136.
Mu ay, H.H.: 2007, Applied Clay Mine alogy: Occu ences,
P ocessing and Applica ion o Kaolins, Ben oni es,
Palygo ski e-Sepioli e and Common Clays. Else ie ,
Ams e dam.
N
eal, M. and Wo al, W.E.: 1977, Mine alogy o Fi eclays:
p
a 1. The c ys alini y o kaolini e in i eclays.
T ansac ions o he B i ish Ce amic Socie y, 76, 57–
61.
Plancon, A. and Zacha ie, C.: 1990, An expe sys em o
he s uc u al cha ac e iza ion o kaolini e. Clay
Mine ., 25, 249–260.
P os , R. e al.: 1989, In a ed s udy o s uc u al OH in
kaolini e, dicki e, nac i e and poo ly c ys alline
kaolini e a 5 o 600K. Clays Clay Mine ., 37, 464–
468.
P ue , R.J. and Webb, H.L.: 1993, Sampling and analysis o
KGa-1b well c ys allized sou ce clay. Clays Clay
Mine ., 41, 514–519.
Russell, J.D. and F ase , A.R.: 1994, Clay mine alogy:
Spec oscopic and chemical de e mina i e me hods.
M.J. Wilson., Abe deen, 11–67.
Sanchez-So o, P.J. e al.: 2000, E ec s o d y g inding o
n
he s uc u al changes o kaolini e powde s. J. Am.
Ce am. Soc., 83 (7), 1649–1657.
Slo ák, V.: 2001, De e mina ion o kine ics pa ame e s by
di ec non-linea eg ession om TG cu es.
The moch. Ac a, 372, 175–182.
Smyka z-Kloss, W.: 1974, Di e en ial he mal analysis:
applica ion and esul s in mine alogy. Sp inge -
Ve lag, Be lin.
T ao é, K. e al.: 2006, Signi icance o kine ic heo ies on
he ec ys alliza ion o kaolini e. The moch. Ac a,
451, 99–104.
kaolini e samples in o wo g oups: o de ed (well
o de ed) and pa ially o de ed. Unano an
d
Olomucany samples we e e alua ed as pa ially
o de ed kaolini e analogous o Sedlec. The cause o
his disc epancy is p obably he p esence o clay
mine al admix u e (e.g. illi e o smec i e), which
s ongly in luences he IR pa e n in OH s e ching
and bending egion. The OH bands a e o e lapped and
hus may lead o inco ec deeg e o s uc u al o de .
Bu e en hough all h ee used me hods gi e a sligh ly
di e en dis ibu ion o he s uc u e classi ica ion, he
o de espec i ely he esul ing end o dec ease in
o de liness is he same o all h ee me hods: KGA-1b
(wi h he bes o de liness) > Jimliko > Sedlec >
Olomucany > Unano (wi h he wo s o de liness).
ACKNOWLEDGEMENTS
This s udy was suppo ed by he Czech Science
Founda ion, he p ojec No.105/08/1398 an
d
N
o.105/07/P416, and by Resea ch plan No. AVOZ
30860518. The au ho s would like o hank Geo ge
Layn o con olling and co ec ing he use o English
in his a icle.
REFERENCES
Apa icio, P. e al.: 2006, A new kaolini e o de index base
d
on XRD p o ile i ing. Clay Mine als, 41 (4), 811–
817.
Apa icio, P. and Galán, E.: 1999, Mine alogical in e e ence
on kaolini e c ys allini y index measu emen s. Clays
Clay Mine ., 47, 12–27.
Be ezni ski, J. e al.: 1998, Adso p ion cha ac e iza ion o
wo clay mine als Socie y S anda d Kaolini es. Jou nal
o Colloid and In e ace Science, 205, 528–530.
B iga i e al.: 2006, S uc u es and mine alogy o clays
mine als. Handbook o Clay Science : De elopmen s
in Clay Science, 1, 19–86.
B indley, G.W. e al.: 1963, Mine alogical s udies o
kaolini e-halloysi e clays. The Ame ican Mine alogis ,
48, 897–911.
B indley, G.W. e al.: 1986, Rela ion be ween s uc u al
diso de and o he cha ac e is ics o kaolini es and
dicki es. Clays Clay Mine ., 34, 233–249.
Chmielo á, M. and Weiss, Z.: 2002, De e mina ion o
s uc u al diso de deg ee using an XRD p o ile i ing
p
ocedu e. Applica ion o Czech kaolins. Applie
d
Clay Science, 22, 65–74.
Cicel, B., No ak, I. and Ho a h, I.: 1981, Mine alogy and
c ys allochemis y o clays. SAV, B a isla a.
Főld á i, M.: 1997, Kaolini e-gene ic and he moanaly ical
pa ame e s. Jou nal o The mal Analysis, 48, 107
–
119.
F eeman, E.S. and Ca oll, B.: 1958, The applica ion o
he moanaly ical echniques o eac ion kine ics: The
he mog a ime ic e alua ion o he kine ics o he
decomposi ion o calcium oxala e monohyd a e. J.
Phys. Chem., 62, 394–399.
Gabbo , P.: 2008, P inciples and applica ions o he mal
analysis. Blackwell Publishing L d., Ox o d.
Guggenheim, S. and Kos e an G oos, A.F.: 2001, Baseline
s udies o he clay mine als socie y sou ce clays:
he mal analysis. Clays Clay Mine ., 49 (5), 433–443.
Ha akeyama, T. and Liu, Z.: 1998, Handbook o The mal
DSpace VŠB-TUO
h p://hdl.handle.ne /10084/84630
21/06/2012