(SPAIi\) iB QUALI

DIOPSIDE BASED WHITE PORCELAIN TILES

F. Ka ra and M. Ca va e
Tubi tak Cera mic Resea rch Ce ntre
Anadolu University, Iki Eyl ul Karnpusu, Eskise hir / Tu rke y
INTRODUCTI ON
In th is study, a porcel ain tile bod y containing a substantial amount of alkal ine ea rth
elements was for mulated to form di opside cryst al s (and / or wollastonite crysta ls if
required ) d u ring firi ng. It is thought that less pure raw materials, es pecially clays
containing iron oxide can be used with out substantia lly degrading the whi teness of the
tile since di opside can d issol ve iron in its latti ce by substit uti ng for magnes iu m.
EXPERIMENTAL
The porcelain body wa s fo rmulated by using a frit , Ukrainian clay, quart z, albite,
calcite and a lte red magnesite. The compositional range of the body is given in Tabl e I. The
tri t was ad ded in order to facili tate easy sintering d uring fast firi ng. Although any type
of frit ca n be used, a d iopside formi ng fri t was d evel oped in order to obtain maximum
d iopside formation d uring firing . The frit containe d 5iO" Ca O, and Kp . Industrial
melting of the fri t was carri ed out in a rota ry furnace at I-tOO"C.
65- 75
AhO,
7- 12
CaO
16- 12
M O
4- 10
Na,O
1-3
K,O
1-3
Fc, O, TiO.!
0.30-0.35
The crys ta lline phases that developed during firi ng of the bod y were characterised
by X-ra y d iiiracti on (XRD) and sh rinkage behaviour was followed by a di latometer. The
microstr uct u re of the sintcrcd porcel ain ti le was investigated usi ng ZI scanning electron
microscope. For ind ustrial production trial s, 30 tons o f s pray d ried granules we re
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ill QUAU 2002

prepared and 330x330 mm and 300x600 mm size tiles were pressed at 40 MPa . These tiles
were sintered at a peak temperature of 121O"C in an industri al roller kiln for 55 min and
65 min for 330x330 mm and 300x600 mm size tiles, respective ly.
RESULTS
The XRD spectrum of the frit after crys tallisation at 11 30"C in a fast firing furnace
and that of the porcelain tile after sinter ing at 121O"C are given in Fig. 1. Frit crys tallises
mainl y to diopside but some amount of cristobalite also occu rs (Fig. l a). The porcelain tile
bod y contains di opside and quartz as main phases but a trace of cris tobalite is also present
(Fig. Ib).
' bl
.,

I'
__.._;J
r(lco
eCC<I
' 000
t
;;
, 1\
c,
4000
'"
;;;
c
Cll )000
E
c
.J
2000
a '\
I VJL
10 0 0
.J'../'-.
.,
'"
es
"
2 Theta [deg)
C" costcoeme. Q" quartz. unmarked peaks receesem eccsee.
Fi,,-: un' 1. XRD :,palra (a' the dio!,o:.idt>jorlllill,!\ f fit aftt'r crystal/isatiol/ at 1150C (iJ) tilt' porcebnn tilt' aftt" siutt'rillS at
1215 C.
.e
o
30
Time(h)
t c
r-- - --- - - - ----- - - - --- - ----- - ---, 2
"'--- - - --- - - - - - - - - - - - - - - - - - - - - - -----' -to
80
u oo
1200
100 0
f5
80 0

' 00
"
w
c.
.,0
E

ace
0
0
Figure 2. Shrillkas t' bchm.'itlur the di0l':,idl' pMeda i".
1\ ,.. 102
Fig. 2 shows the shrinkage be haviour of the body. There are two vol ume expans ions:
one is at 573"C and the other sta rts at about 1000"C and conti nu es until the onset of
shrinkage at lI20"C. The expans ion seen at 573"C is d ue to the well kn own u-{) qu artz
tr ansformatio n whereas that starti ng at l OOO"C is tho ug ht to res ult from the vo lu me
expansion due to the forma tion of diopsidc from the reacti on of a mixture of qu artz,
magne sium and calcium oxi des. The amount of vo lume expansion d ue to di opsi de
formation is O. 5j{. Before thi s volume expansion, 0.3% volume shrinkage is also evidenced
at around 900"C in Fig. 2. This is att ribu ted to diopside crystallisation fro m the frit. The
di opside crystals formi ng from the fri t act as seeds for furt he r d iopside formation from the
reaction of quartz, magnesium and calcium oxides . Total linear shrinkage was observed
to be 9.5%. Th e SEM micrograph of the sintered tile afte r light etching wit h HF is shown
in Fig. 3. Diopside and quartz crysta ls are embedded in a glassy ma trix. The size of the
d iopsi de cr yst als is less than I .L1m. Some prope rties of the po rce lain ti le prod uced on an
ind ustr ial sca le are listed in Table 2.
Dry strength (kg/em') 13
Fired strength (kg/em') (ISO 10545-4) 615
Water absorption (%)( ISO 10545-3) O.O:!
Thermal expansion coefficient (ISO 10545-8) 6.76x l O-!l
Deep abrasion resistance {mm") (ISO 10545-6) 131
Chemical resistance (ISO 10545-13) UIIA
Colour L ~ 9 5 5 a- -0.56. b- 5.47
The fire d st rengt h of th e new ti le is so mewha t higher than that of commercial
porcelain tiles, which lies be tween 500-550 kg / cm. Th is can be att ributed to a large
am ount of di opside formati on in the composition. Whi ten ess of the tile is also qui te hi gh .
In order to observe the effectiveness of di opside crysta ls on whiteness, a diopside forming
compositio n and a trad itional porcel ain tile composition were prepared with the same
amount of 1'1.',0, (0.33jt,,) and TiO, (0.327<,). The colour values of the di opside form ing
composi tion were L=89,63, .1=-0.37, b=7,50, whereas those of th e tr aditi onal porcelai n tile
composi tion were L=8 1, 13, .1 =-1.21, b=7,96. Thi s is believed to be due to the fact that iron
ions are substi tuted for magne si um ions in the di opside latti ce and thus they have the
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Jill QUAU / 2002 CASTELLO" (SI'AI:-I)
valency of +2. [ron ions with --2 valency do not cause colouring. Deep abrasion resistance
is also better than that of comme rcial porcelain tiles, whi ch varies between 139-147 rnrn' .
Similarly to the mechani cal properti es, a large amount of di opside crys tals improves
abrasion resi stance.
CONCLUSIONS
A diopsi de based new porcelain tile has been developed . Thi s new tile can be
produced with high whiteness compa red to conve ntional tiles wh en the sa me amo unt of
impurities is present in the compos ition. Thus, relat ively impure raw mat eri als can be
tolerat ed when prod ucing tiles with hi gh whiteness. The new tile is mechani call y stronger
with higher abras ion resistance. Depending on the CaO/ MgO rati o in the starting
compos ition, diopside, di opside-wol lastoni te and woll astonite conta ini ng tiles can be
produced.
Po.; - 1M