Original papers

CRYSTALLIZATION BEHAVIOUR
OF FLUORPHLOGOPITE GLASS CERAMICS
ESMAT M.A.HAMZAWY

Glass Research Department

National Research Centre,
12622 Dokki,
Cairo, Egypt
E-mail: [email protected]

Received February 7, 2000 ; accepted February 20, 2001.

Transparent fluorphlogopite based glasses were prepared using talc, glass sand and phosphate raw material. The effect of
TiO2, ZrO2, phosphate or combinations of either B2O3-phosphate or TiO2-ZrO2 on the crystallization of fluorphlogopite base
glass was examined. X-ray diffraction analysis showed formation of fluorphlogopite at 765 °C in the base glass. Addition of
ZrO2 or 5 wt.% phosphate did not affect the monophase crystallization. However, when the amount of phosphate was
increased to 10 wt.%, fluorapatite was crystallized together with fluorphlogopite. TiO2 and TiO2-ZrO2 addition enhance the
formation of enstatite together with fluorphlogopite. Thermal treatment of ZrO2-containing glasses was found to induce
crystallization of fluorphlogopite as a main phase. The addition of TiO2 alone or mixed with ZrO2 catalyzed crystallization of
enstatite and fluorphlogopite above 1000 °C. SEM analysis showed that glasses containing fluorphlogopite acquired fine-
grained microstructure at 650 – 765 °C. At higher temperature, 1000 °C, the crystal structure of fluorphlogopite was modified
into interlocked flakes. Vicker’s hardness values of the glass-ceramics increased in presence of enstatite (7358 MPa) and
decreased in the presence of fluorapatite (4905 MPa). Addition of B2O3 decreased the density of glass to 2.634 g/cm3 and
glass-ceramic to 2.780 g/cm3 . Phosphate or ZrO2 additions showed a reverse effect (2.864 g/cm3). Thermal expansion
coefficients of fluorphlogopite glass-ceramic samples in temperature range 20 - 500 °C changed from 7.8 × 10-6 °C -1 in
presence of fluorapatite to 9.2 × 10-6 °C -1 in case of the dominance of enstatite.

Keywords: Glass-ceramics, Fluorphlogopite, Eustantite, Fluorsilicate glasses

INTRODUCTION were measured and related to the type, concentration

and microstructure of the crystalline phases formed.
The importance of glass-ceramics, in general, is
derived from the advantages of being produced by EXPERIMENTAL PART
conventional glass-forming techniques followed by
controlled crystallization [1, 2]. The fluorphlogopite The raw materials used include talc, glass sand and
glass-ceramics are characterized by their unique phosphate, which is composed mainly from fluorapatite
physical properties; in particular, cleavage, flexibility Ca5(PO 4) 3F. The chemical analyses of these raw
and elasticity. These properties are unique among glass- materials are shown in table 1. Other additives, i.e.
ceramics because such glass-ceramics can easily be K2CO3, H2BO3 and MgF2 were introduced as minor
worked on machines [3, 4]. In addition, these materials components. TiO2 or ZrO2 and their mixtures were
enjoy fracture resistance, thermal shock-resistance, and tested as nucleating agents for the base glass.
have excellent dielectric properties [5]. Recently, the The principal type of glass studied was the
former properties were improved by control of either fluorphlogopite base glass, which had the
orientation [6], or the grain size and morphology [7] of KMg2.5Si4O10F2 stoichiometric formula (G0). This glass
the crystalline phase formed in mica glass-ceramics. was prepared from talc, glass sand, MgF2 and K2CO3.
These exceptional properties give such glasses prefe- This basic composition was modified by the addition of
rence in several fields of application [8]. phosphate raw material to replace 5 or 10 wt.% of
The fluorphlogopite glass-ceramics can be fluorphlogopite base glass. In addition, a mixture of
produced from low cost abundant natural raw materials. equal amounts of phosphate material and B2O3 was
The present investigation deals with the effect of some introduced to replace 10 wt.% of the fluorphlogopite
combinations and some additives on the type of base glass. The chemical compositions of the glasses
crystalline phases developed in tetrasilicic mica prepared are shown in table 2.
glasses. The density, microhardness and thermal The appropriate amounts of powdered glass batch
expansion coefficient of the obtained glass-ceramics materials and chemicals were well mixed and melted in

Ceramics − Silikáty 45 (3) 89-96 (2001) 89

 E. M.A.Hamzawy

Table 1. Chemical composition of the raw materials (wt.%).

raw material SiO2 Al2O3 Fe2O3 CaO MgO K 2O Na2O P 2O 5 I.L

talc1 62.00 1.60 0.40 0.40 30.30 0.11 0.32 - 4.7

phosphate2 11.19 0.66 1.83 45.43 0.20 0.10 0.86 29.44 1.66
sand3 99.2 0.28 0.03 0.10 - - - - -

1 Hamata,Eastern Desert, EGYPT.

2 Sibaya,
Western Desert, EGYPT.
3 Abu Zenima, Sinai, EGYPT.

Table 2. Chemical composition of glasses prepared (wt.%).

Glass Constituents Glass No.

G0 G1 G2 G3 G4 G5 G6

SiO2 57.81 54.52 52.14 51.13 57.81 57.81 57.81

Al2O3 0.77 0.79 0.72 0.77 0.77 0.77 0.77
Fe2O3 0.19 0.33 0.32 0.46 0.19 0.19 0.19
CaO 0.19 3.62 3.63 7.06 0.19 0.19 0.19
MgO 14.55 14.00 12.76 12.60 14.55 14.55 14.55
K 2O 11.37 10.50 10.01 10.05 11.73 11.73 11.73
Na2O 0.16 0.22 0.19 0.25 0.16 0.16 0.16
P 2O 5 - 2.23 2.24 4.47 - - -
MgF2 14.95 13.81 13.16 13.21 14.95 14.95 14.95
B2O 3 - - 4.83 - - - -
TiO2* - - - - 2.00 - 2.00
ZrO2* - - - - - 2.00 2.00

* Amount added to 100 wt.% of glass batch.

covered platinum crucibles for 3 hours at a temperature determined by Linseis dilatometer (model L76/1250)
in the range 1350 - 1450 °C. After melting, the glass using a heating rate of 5 °C/min.
melts were cast into rods and patties, which were
subsequently annealed at 500 °C for 15 min, and left to RESULTS
cool inside the muffle furnace which was switched off.
The differential thermal analyses (DTA) were Crystallization of the base glass
performed using a Shimadzu, DT 30 apparatus. 70 mg
of granular glass samples (0.25 - 0.60 mm) were used. The heat-treatment, according to the DTA results
The heating rate applied was 10 °C/min. The XRD (figure 1 and table 3), brings the formation of crystalline
spectrometer, Philips 1390, Cu-target Ni- filter, was fluorphlogopite phase alone at a low heat-treatment
used for the identification of crystalline phases temperature (765 °C). The transparency of the base
developed after heat treatment. Microhardness was glasses is slightly reduced by the formation of the
measured on polished crystalline samples using fluorphlogopite phase. The transparency of the glass
Vicker’s microhardness indenter (Shimadzu, type-M, changed to white translucent material when the glass
Japan). The densities of glass and glass ceramic samples was heat-treated at 898 °C. This effect was associated
were determined at room temperature by the with the crystallization of enstatite phase. At still higher
Archimedes method using xylene. The arithmetic mean temperatures (1000 °C, 10 hours), a white opaque glass-
of three readings for each sample was calculated. ceramic was developed and fluorphlogopite decompo-
Representative SEM micrographs were obtained sed partially to the enstatite becoming the major phase
for gold coated freshly etched crystalline samples using at very high temperature (1100 °C, 5 hours, table 4).
SEM Philips XL30. The SEM micrograph of the former transparent
The coefficients of thermal expansion of glass- crystallized glass shows a fine microstructure of the
ceramic samples (dimension 0.3 × 0.3 × 1.6 cm) were monocrystalline fluorphlogopite phase in minor glassy

90 Ceramics − Silikáty 45 (3) 89-96 (2001)

 Crystallization behaviour of fluorphlogopite glass ceramics

matrix (figure 4). However, the microstructure of all

other glass-ceramic materials, with or without any
additives, could not be viewed under the polarizing
microscope magnifications.

Effect of phosphates on base glass

The XRD analysis of G1 sample having lower

phosphate content treated at 755 °C (the first
exothermic temperature) shows the growth of
transparent monophase of fluorphlogopite, the same as
in the base glass. This phase crystallized with enstatite
(G2) or fluorapatite (G3). The second exothermic
peak reflected the crystallization of fluorapatite (G3,
bearing higher phosphate content). However, the second
and third exotherms in G2 and G3 showed only the
formation of the fluorphlogopite, enstatite and
fluorapatite phases (table 3). Treatment at higher
temperature showed an increase in the crystallinity but
with relative decrease in fluorinated phases contents
(figure 3 and table 4).
It should be noted that the softening and
exothermic peak temperatures observed for these
glasses decreased with an increase in the phosphates
addition (nominal fluorapatite) (figure 1). The
introduction of B2O3 to phosphate-containing glass (G2)
lead to the development of another exothermic peak
(compare G0, G1&G2, table 3).
Figure 1. DTA thermograms of some investigated glasses. The SEM micrograph of the white G3 sample heat-
treated at high temperature (1000 °C/10 hours) shows

Table 3. Results of crystallization behaviour of glass samples.

glass peak crystalline phases formed transparency of glass

no. temp. (°C)

G0 650 amorphous*. transparent glass**.

765 formation of fluorphlogopite. transparent glass with faint opacity
898 formation of enstatite translucent white opalescence
G1 650 * **
755 formation of fluorphlogopite. transparent glass with faint opacity
890 co-crystallization of enstatite & fluorapatite white translucent
G2 640 * **
775 co-crystallization of enstatite &fluorphlogopite light white translucent opal
835 formation of fluorapatite white translucent opal
950 crystallization increase of enstatite & fluorapatite translucent dark opal
G3 630 * **
715 co-crystallization of fluorphlogopite&fluorapatite semi-transparent white opal
835 crystallization increase of the former phases opaline
G4 680 * **
755 co-crystallization of fluorphlogopite &enstatite whitish-translucent
890 crystallization increase of enstatite white translucent
G5 700 * **
818 formation of fluorphlogopite transparent glass with faint opalescence
910 crystallization of enstatite translucent opal
990 crystallization increase of enstatite white translucent opal
G6 680 * **
775 co-crystallization of fluorphlogopite &enstatite white translucent
890 crystallization increase of enstatite like the above

Ceramics − Silikáty 45 (3) 89-96 (2001) 91

 E. M.A.Hamzawy

Figure 3. XRD patterns of G0, G1, G2& G3 glasses heat-treated

at 1000 °C for 10 hours.
! - fluorphlogopite, " - fluorapatite, ! - enstatite.

Figure 2. XRD patterns of G0, G4, G5& G6 glasses heat-treated

as indicated on figure.
! - fluorphlogopite, ! - enstatite.

interlocked flakes of fluorphlogopite with enstatite and

fluorapatite (figure 5).

Nucleation in base glass

The XRD patterns of the heat-treated glasses at

each endothermic and exothermic peaks or at a higher
temperature, 1000 and 1100 °C showed the effect of
TiO2 (G4) in catalyzing the fluorphlogopite and pyroxe- Figure 4. SEM of G0 glass heat-treated at 650 °C for 1 hour and
ne crystallization especially at higher temperatures at 765 °C for 3 hours, show spread of fluorphlogopite micro-
(figure 2, table 4). At the first exotherm of G4 (755 °C), crystalline structure in little glassy matrix.
the incorporation of TiO2 enhanced the crystallization
of enstatite in addition to fluorphlogopite, which
crystallized as monophase in the base glass at 765 °C. d-lines of enstatite at the expense of the fluorphlogopite
The temperature increase to 890 °C (G4, the second (compare crystallization of G4 in figure 2). The later
exotherm), lead to an increase in the intensities of X-ray results showed the role of TiO2 in catalyzing the

Table 4. Crystalline phases developed at higher temperatures as detected by XRD analysis.

glass G1 G2 G3 G0 G4 G5 G6

heat- phases present

treatment (°C/h)
1000/10 FP+EN+FA EN+FP+FA FP+FA+EN FP+ EN EN+FP FP+EN EN+FP
1100/5 FP+EN+FA EN+FP+FA FP+EN+FA EN+FP EN+FP FP+EN EN+FP

FP - Fluorphlogopite, FA - Fluorapatite, EN - Enstatite.

92 Ceramics − Silikáty 45 (3) 89-96 (2001)

 Crystallization behaviour of fluorphlogopite glass ceramics

a)

Figure 5. SEM of G3 glass heat-treated at 1000 °C for 10 hours,

shows the growth of the main fluorphlogopite interlocked
flakes with fluorapatite and enstatite.

crystallization of pyroxene, which also depicted in the

crystallization at higher temperatures (i.e. at 1000 and
1100 °C of G4 and G6 samples table 2). On the other
hand, ZrO2 enhanced the fluorphlogopite as the major
phase under wide range of heat-treatment temperatures.
b)
This was shown either in crystallization of fluorphlo-
gopite alone (in G5 at the first exotherm i.e. 818 °C,
figure 2) or its persistence as the main phase at Figure 6. Schematic representation of calculated glass and
higher temperatures (table 4). Similar effect increasing glass-ceramic densities,
the pyroxene over the fluorphlogopite at higher tempe- a) combined with phosphate,
rature was also observed when TiO2 mixed with b) nucleated by TiO2, ZrO2 and TiO2-ZrO2. " - Glass, # - glass
ZrO2 (G6). heat-treated glass at 1000 °C for 10 hours, ! - glass heat-treated
When looking into the DTA thermogram, the glass at 1100 °C for 5 hours
addition of TiO2 (G4), ZrO2 (G5) or their mixture TiO2-
-ZrO2 (G6) to the parent glass shifted the endothermic
and the exothermic peaks to higher temperatures increased in the same way as that of glass. Due to the
especially in case of ZrO2 addition (figure 1). partial decomposition of the fluorphlogopite to
enstatite and glassy phase, the densities of the resultant
Density glass-ceramics, in particular those containing
B2O3 decreased at higher temperature i.e 1100 °C
The density of the base glass varied significantly (figure 6a).
with the addition of phosphate, B2O3 or TiO2, ZrO2 and
their mixture. Figure 6 shows the densities of glasses Microhardness
and glass-ceramics formed at given temperatures.
In glass, the density increased with an increase in The Vicker’s hardness values of the glass-ceramics
phosphate content. The smallest increase in (developed after heat-treatment at DTA temperature
density was observed for glass G2 containing 5 wt.%. peaks) showed continuous decrease with increase in the
Density of the corresponding glass-ceramics, compared phosphate addition (i.e. fluorapatite content). This value
to that of the base glass, increases with heat-treatment at ranged from 6082 MPa (base glass) to 4905 MPa (G3).
1000 °C in a way similar to glass, with the exception In case of the added nucleants, the value increased up to
of G2 (containing 5wt.%) of the lower value. On the 7358 MPa (G6) as the pyroxene crystallization took
other hand, an increase in the heat-treatment place.
temperature to 1100 °C decreased density relative
to those of glass-ceramics obtained by heat-treatment Thermal expansion
at 1000 °C. The greatest decrease in density was
observed for glass G2. The addition of nucleating For the samples heat treated at 1100 °C, marked
agents increased the density in the following order: changes in the thermal expansion occurred depending
TiO2 + ZrO2, (G6) > ZrO2, (G5) > > TiO2, (G4) > G0. The on the type of both the major and minor crystalline
density of the corresponding glass-ceramics also phases formed. Table 5 shows that the thermal

Ceramics − Silikáty 45 (3) 89-96 (2001) 93

 E. M.A.Hamzawy

Table 5.. Thermal expansion coefficient of glass samples heat crystallization. However, the proposed nucleation
treated at 1100 °C for 5 hours. mechanism mentioned before [11], which has been
supported recently [12] may depict the sequence of
glassno. thermal expansion identified crystallization. This means that, the introduced
coefficient (10-6C-1) phases constituent in glass batch increase the rate of nucleation
and decrease the interfacial energy between the crystals
20-300 °C 20- 500 °C and glass. In other words, the sequence of
fluorphlogopite crystallization may be expressed as:
G0 9.2 9.1 EN+FP Fluophlogopite glass {heat-treatment at nucleation
G1 7.6 7.8 FP+EN+FA
temperature} → Separated nuclei of Mg and F rich
phases {treatment at crystallization temperature}
G2 7.7 7.9 EN+FP+FA
→ Fluorphlogopite crystals + Residual glass.
G3 8.6 8.7 FP+EN+FA
When looking for the effect of combined samples
G4 8.9 9.2 EN+FP
with phosphate and B2O3, some previous work can
G5 8.4 8.9 FP+EN depict their actions. The higher field strength of P5+
G6 9.0 9.2 EN+FP (2.1) ions compared with Si4+ (1.57) ions cause drainage
of the Mg, Al, alkali cations and fluorine ions from the
silicate droplet [10]. Due to this strong effect, the lower
percentages of combined phosphates in base
expansion coefficient decreased with formation of composition yield easily fluorapatite. This amount of
fluorapatite (G1, G2& G3) and increased under the crystallized fluorapatite increases with the addition of
dominance of the enstatite (G0, G4). phosphates when it compensates usually major phase
fluorphlogopite. On the other hand, B3+ (ionic radius =
DISSCUSION = 0.020 nm and atomic weight = 10.81) ion can be
expected to enter the tetrahedral layer (substituted for Si
The internally fluorine-nucleated fluorphlogopite of ionic radius = 0.041 nm and atomic weight = 28.09)
component, lead to the reduction of the viscosity of the in phlogopite [13]. Other results show that B2O3 in
melt. The presence of fluorine ions facilitates the trisilicic mica may be replaced by ~10 wt.% Al2O3 [5].
mobility of structural elements in glass and enhances These data can depict the distinct lower density in the
the fluorphlogopite crystallization. Due to these present samples. Another noticed effect of boron
combined factors, transparent glass-ceramic material of addition is the coexistence of F-free and F-containing
nearly single phase resulted from heat treatment at 755- phases resulting from the effect of lower viscosity of
818 °C. This transparency reflects the ultra-fine glass melt and subsequent higher ions mobility during
microstructure and the similarity of the refractive heat-treatment.
indices of the monophase fluorphlogopite and the The influence of the nucleants added was studied
remaining residual glass. by many authors [13 - 15]. Solubility of ZrO2 in the
Literature survey proposed different concepts to glass melt reaches 4 wt.% [14]. Other authors have
explain the mechanism of fluorphlogopite glass found that ZrO2 addition of 8 wt.% leads to the
crystallization. Daniel and Moore [8] show that crystallization of tetragonal ZrO2 and fluorphlogopite
crystallization of fluorphlogopite glass takes place in and suppressed other silicate phases [15]. In agreement
two stages: (i) Initial structural ordering which occur at with these results, ZrO2 addition investigated in this
~600 °C. The value of the transformation temperature work supports the fluorphlogopite crystallization and
depends on the fluorine content. (ii) Crystal morpho- decreases the amount of silicate phases formed. TiO2
logy of the glass-ceramic changes from 900 to 1150 °C. additions induce mica growth [15 - 17] and the higher
Chung et al [5] suggested a complex multi stage percentages tend to form titanate phases [15]. However,
sequence for crystallization: (a) heterogeneous the lower amount of TiO2 in our samples (even those
nucleation of BCC chondrodite (Mg5Si2O8F2)–like mixed with ZrO2) has strong effect on the usual
crystals in glass matrix, (b) re-crystallization of dominant enstatite crystallization especially at higher
chondrodite to norbergite (Mg3F2SiO4), (c) epitaxial temperatures.
growth of fluorphlogopite. Others added that the The values of thermal expansion coefficient vary
thermal treatment increase fluorphlogopite content considerably with both the temperature range used and
and decreases chondrodite and norbergite amount the contents of developed phases. In previous glass-
observed at temperatures above 800 °C [9, 10]. Recent ceramic works, the measured thermal expansion
work [6] by Habelitz et al. mentioned that norbergite coefficient was 6.4 - 7.1 × 10-6 °C-1 for fluorphlogopite
serve as a fluorine reservoir for the fluorphlogopite [18], and was 7.4 - 11.9 × 10-6 °C-1 for fluorapatite [19],
formation. where it was 7.5 - 10.0 × 10-6 °C-1 for enstatite [20]
The aforementioned phases chondrodite and (20 - 300 °C). In the present investigation, the thermal
norbergite were not detected in the present samples. expansion coefficient of the glass ceramics was
These phases may be separated in the glassy state which practically influenced by the type and the concentration
act as nuclei for subsequent fluorphlogopite of combined phosphate and nucleant used which had a

94 Ceramics − Silikáty 45 (3) 89-96 (2001)

 Crystallization behaviour of fluorphlogopite glass ceramics

significant on the resulting crystalline phases (table 5). References

These expansion coefficients were a composite of the
percentages of low-expansion phases and the high- 1. Partridge G.: Glass Technol. 35, 171(1994).
-expansion ones (usually includes the residual glass). 2. Holand W., Vogel.W., Mortier W.J., Duvigneaud
However, depending on the substitution of phosphates P.H., Naessens G Plumat E.: Glass Technol. 24, 318
in the parent sample, the thermal expansion coefficient (1983).
change from 9.1 in the base glass to 7.8 × 10-6 °C-1 3. Copp A.N.: Ceram. Bull. 75, 138 (1996).
(20 - 500 °C) in glass containing lower amount of 4. Beall G.H. in: Advances in nucleation and crystallization
phosphate (5 wt. %). On the other side, addition of in glasses, p. 251, Ed. Hench L.L. and Freiman S.W.: Am.
TiO2 alone or admixed with ZrO2 increases the thermal Ceram. Soc., Columbus 1971.
expansion coefficient to 9.2 × 10-6 °C-1 (20 - 500 °C). 5. Chung K., Beall G.H., Grossman D.G: Proc. Xth Int.
The comparison of the expansion coefficient as the Congress on Glass, p.122, Tokyo 1974 .
function of the developed phases in fluorphlogopite 6. Habelitz S., Carl G., Russel G., Kurt M., Roeder E., Eifler
glass ceramic samples shows that when enstatite D., Hergt R.: Glastechn. Ber. Glass Sci. Technol. 70, 86
becomes the major phase the value of thermal (1997).
expansion coefficient increases but the presence of 7. KojimaY., Matsuo K., Nakashima K., Morinaga K.: J.Jpn.
fluorapatite decreases this value. It must be added Inst. Met. 55, 172 (1991).
that the decomposition of fluorphlogopite into 8. Daniel W.H., Moore R. E.: J. Am. Ceram. Soc. 58, 217
enstatite accompanied by residual glass rich in (1975).
potassium, which lead to increase in thermal expansion 9. Teodorscu S., Rusu E.: Mater. Const. 10, 22 (1980).
too. 10. Vogel W., Holand W., Naumann K, Gummel J.: J. Non-
Cryst. Solids 80, 34 (1986).
CONCLUSION 11. Hillig W.B.: Proc. Symp. on nucleation and crystallization
in glasses and melts, p.77, Am. Ceram. Soc., Columbus
The study of crystallization behaviour of fluor- 1962.
phlogopite glasses can be summarized by followed 12. Doremus R.H.: Glass Science. 2nd Ed., p.73-95,
conclusions: A Wiley–Interscience Publication, John Wiley &Sons Inc.
New York 1994.
1. Transparent glass-ceramics of single phase 13. Stubican V., Roy R.: Am. Min. 47, 1166 (1962).
fluorphlogopite was prepared. 14. Mc Millan : Glass-Ceramics, 2nd edition, Academic Press,
2. The addition of phosphates enhanced the formation New York 1979.
of fluorapatite, in compensation of fluorphlogopite 15. Saraswati V.: J. Non Cryst. Solids 124, 254 (1990).
contents, which decreased at higher temperatures. 16. Carl G. : Proc.17th Int. Cong. on Glass, Vol.5, p.343-348,
3. The addition of B2O3 decreases the viscosity of Beijing 1995.
glass making possible the coexistence of the 17. Xie J.L., Feng H., Wenhuba S.: Glass Technol. 37, 175
dominating enstatite and the F-containing phases at (1996).
all heat-treatment regime used. 18. Grossman D.G.: J. Am. Ceram. Soc. 55, 446 (1972).
4. ZrO2 additions induce fluorphlogopite crystal- 19. Vogel W., Holand W., Naumann K.: J. Non. Cryst. Solids
lization as predominant phase. 80, 34 (1986).
5. The addition of TiO2 or mixture with ZrO2 induces 20. Echeverria L.M., Beall G.H.: Glass Trans. 20, 244 (1991).
the enstatite and fluorphlogopite formation, with
predominance of the enstatite particularly at high
temperatures.
6. Density trend of glasses and glass-ceramics
increases in direction of TiO2+ZrO2 addition >ZiO2
addition >TiO2 addition >base glass. Glass and KRYSTALIZAČNÍ CHOVÁNÍ FLUORFLOGOPITOVÉ
glass-ceramic in B2O3 –containing sample show SKLOKERAMIKY
lower density than other samples.
ESMAT M.A.HAMZAWY
7. Microhardness values increase up to 7358 MPa
when enstatite is dominating phase and decreases Glass Research Department,
to 4905 MPa when fluorapatite phase is National Research Centre
developing. 12622 Dokki, Cairo, Egypt
The thermal expansion coefficient of fluorphlo- Byla připravena transparentní fluorflogopitová skla s po-
gopite glass-ceramic samples increases to 9.2 × 10-6 °C-1 užitím mastku, sklářského písku a fosforečnanů. Dále byl
in presence of enstatite as a major phase, but decrease to sledován účinek přídavků TiO2, ZrO2, fosforečnanů nebo
7.8 × 10-6 °C -1 (20 - 500 °C) in case of crystallization kombinací B2O3-fosforečnan a TiO2-ZrO2 na krystalizační
the fluorapatite. chování základního fluorflogopitového skla. RTG difrakční
analýza prokázala tvorbu fluorflogopitu při 765 °C v základ-
ním skle. Přídavek ZrO2 nebo 5 hmotn.% fosforečnanu

Ceramics − Silikáty 45 (3) 89-96 (2001) 95

 E. M.A.Hamzawy

neovlivnil monofázovou krystalizaci. Zvýšený přídavek (1000 °C) se krystalická struktura fluorflogopitu změnila na
10 hmotn.% fosforečnanu však vedl ke společné krystalizaci formu vzájemně spojených šupinek. Hodnoty mikrotvrdosti
fluorapatitu a fluorflogopitu. TiO2 a TiO2-ZrO2 přídavky sklokeramiky vzrostly za přítomnosti fluorapatitu (4905 MPa).
zvýšily tvorbu enstatitu spolu s fluorflogopitem. Ohřev skel s Přídavek B 2O 3 snížil hustotu skla na 2,634 g cm -3 a
přídavkem ZrO2 indukoval krystalizaci fluorflogopitu jako sklokeramiky na 2,780 g cm-3. Přídavek fosforečnanů a ZrO2
hlavní fáze. Přídavek samotného TiO2 nebo ve směsi se ZrO2 měl opačný účinek (2,864 g cm -3). Koeficient teplotní
podnítil krystalizaci enstatitu a fluorflogopitu nad 1000 °C. roztažnosti vzorků fluorflogopitové sklokeramiky dosahoval
SEM analýza ukázala, že skla obsahující fluorflogopit měla hodnot 7,8 × 10-6 °C-1 za přítomnosti fluorapatitu a 9,2 ×
jemnozrnou strukturu při 650 až 765 °C. Při vyšší teplotě × 10-6 °C-1 v případě dominujícího enstatitu.

Ceramics − Silikáty 45 (3) 89-96 (2001) 96