JOURNAL Oi-

NON-GRWAUNESOL
ELSETIER Journalof Non-CrystallineSolids 196(1996)346-35 1

Apatite-mullite glass-ceramics
A. Clifford, R. Hill *
Department ofMuteria1 Science and Technology, University oflimerick, Linrerick, Ire/ad

Abstract

Two series of glasses based on (2 - x)%0,. xP,O, . Al,O, . CaO . yCaF, were studied. The values of s and y were
varied from 0 to 1. The nucleation and crystallisation processesthat occurred in these glasseswere measured. Glasses in
which x= 0.5 and y was greater than 0.5 crystallised to fluorapatite and mullite. Crystallisation occurred by a bulk
nucleation mechanism involving prior amorphous phase separation. The glass with x = OS and y =I 0.5 was converted to a
ceramic to give a material consisting of elongated fluorapatite crystals that had high fracture toughness.

1. Introduction the apatite-wollastonite, AW system [3], which can

There is considerable interest in apatite-based ma-
terials for dental and medical applications [ll. Most
research has been directed towards the development
of hydroxyapatite (HA) based materials produced by
a sintering route. However, there are problems en-
countered on sintering HA, notably arising from
degradation at high temperature [2]. All the sintered
HA materials lack sufficient strength and toughness
[2]. Furthermore, sintering is not an attractive route
for the production of the complex shapes required
for substitute bone parts, or dental ceramics.
Glass-ceramics represents an alterative production
route for apatite-based materials offering the ability
to cast components in the glassy state directly to the
required shape. However, the most extensively stud-
ied glass-ceramic for potential use as a biomaterial is
* Correspondingauthor. Tel: +353-61 202 626. Telefax:
+353-61 338 172.E-mail: hill@ul.ie.
not be cast to shape and is processed by a sintering
route. It is often stated that the apatite is fluorapatite
(FAP), but the glasses studied are very deficient in
fluorine with respect to the fluorapatite stoichiometry
[3]. It is likely, therefore, that the apatite formed is a
mixed fluoro-, hydroxy-, or oxy-apatite. The AW
system has a marked surface nucleation of both the
apatite and wollastonite phases [3,4], and this is one
of the reasons why materials based on this system
are produced by a sintering route.
Recently Hill et al. [5] developed a readily castable
glass-ceramic from the SiO,-Al,0 ,-P,O,-CaO-
CaF, system as a result of research undertaken on
ionomer glasses [6-81. Dimitrova-Lukacs et al. [9]
have demonstrated that one of the compositions stud-
ied by Hill et al. when converted to a ceramic gives a
material with high fracture toughness and high
strength. The high fracture toughness is thought [5,9]
to arise from the microstructure (Fig. l>, which
consists of interlocking apatite and mullite crystals.
The apatite crystals can have an aspect ratio greater
than 50 and, during fracture, these needle-like crys-

0022-3093/96/S15.000 1996ElsevierScienceB.V. All rights reserved

SSDI 0022-3093(95)0061 t-7
 A. Clijj?ord, R. Hill/Journal
tals are pulled out giving rise to a high fracture
toughness 191.
Jana and co-workers [ IO,1 l] and King et al. [12]
have similarly investigated the crystallisation of
ionomer glasses but the compositions they studied
are prone to loss of fluorine during melting, and no
data are available on their nucleation behaviour or
their suitability for forming monolithic glass-
ceramics. Furthermore, these studies are directed
towards use of partially crystalline glass powders for
use in polyalkenoate(ionomer) cement formation. The
glass compositions studied by King et al. [12] con-
tain less than 1% fluorine by weight after firing,
compared with an intended fluorine content of 5%.
Jana and co-workers [lo,1 l] unfortunately do not
give detailed compositional information on the
glasses they studied.
2. Experimental procedures
2.1. Preparation of the glasses
The glass components silica (SiO,), alumina
(Al,O,), phosphorous pentoxide(P,O,), calcium car-
bonate (CaCO,) and calcium fluoride (CaF,) were
weighed in the appropriate ratios to give approxi-
Fig. I. Elongated FAP crystal exposed in a fracture surface.
ofNon-Crystalline Solids 196 (19961346-351 347
mately 500 g of glass, then mixed for 2 h in a ball
mill. The resulting mixture was transferred to a
mullite crucible and vacuum dried prior to firing.
The crucible and charge were heated in an electric
furnace at a temperature between 1350 and 1550°C
depending on composition. After this period, the
glass melt was shock quenched by pouring directly
into demineralised water. The glass frit produced
was then ground in a vibratory mill and sieved to
produce powder for subsequent analysis. Monolithic
glass samples were produced by casting directly into
graphite moulds.
Two series of glasses were prepared based on the
following generic composition: (2 - x)SiO, . xP,Oj
. Al,O, . CaO . y&F, In the first series of glasses,
termed the A series, y was fixed at one and x was
varied from zero to one, while in the second series,
termed the B series, x was kept constant at 0.5 and
y was varied from zero to one. All these composi-
tions contain a basic oxide in the form of CaO,
which has previously been shown [7] to suppress the
loss of volatile silicon tetrafluoride from fluoro-
alumino-silicate glass during melting. In all these
glasses, there is also sufficient calcium to charge
balance the aluminium atoms present and enable
them to occupy up a fourfold co-ordination state
within the glass network.
348 A. CliSford, R. Hill/Journul of Non-Crystalline Solids 196 (1996) 346-351

AT

I 1 I I 1 I 1 1
600 650 700 750 800 850 900 950
Ramp temperature fnC)

Fig. 2. A DTA trace for the glass with x = 0.5 and y = I. Note the sharp glass transition temperature, rg, and the cxothcrm temperatures
corresponding to crystallization.

2.2. Properties of the samples
The samples produced were measured by differen-
tial thermal analysis (DTA) using a Stanton Redcroft
DTA 673-4. to obtain values for the glass transition
temperature, T:, and peak crystallisation tempera-
tures, Tp. The crucibles used were matched pairs
made of platinum-rhodium alloy. Alumina was used
as the reference material. Runs were performed at a
heating rate of 10°C min-’ unless otherwise stated.
The tendency of the glasses to undergo surface nu-
cleation was assessed by performing DSC runs using
three particle sizes; frit, 150 to 45 km and < 45
km.
Activation energies for crystallisation were deter-
mined based on the method of Matusita [13]. The
basis of the method is the relationship between heat-
ing rate and exothermic peak temperature, Tp,
In f”/Tl = - (mE/RT,) = constant,
where ? is the heating rate, E is the activation
energy R is the gas constant and II and 172are
numerical constants depending on the crystallisation
mechanism.
One of the deficiencies of this method is that it
requires prior knowledge of the crystallisation mech-
anism. For example, n = 3, vz = 4 is the case for
bulk nucleation and an increasing number of nuclei,
while n = m = 3 is used for bulk crystallisation from
a constant number of nuclei. Combined DTA/TGA
(Stanton Redcroft DTA/TGA 1600) was used to
study weight changes accompanying crystallisation
processes.
X-ray powder diffraction was performed using a
diffractometer (Phillips PW 1710) using Cu (KU)
radiation on glass samples heat treated at 10°C min- ’
to the temperatures to corresponding to the relevant
Tp, and Tp2. Scanning electron microscopy (Cam-
bridge Stereoscan 90) was carried out on fractured
and polished surfaces after sputter coating with pal-
ladium gold alloy.
 A. Cliflard, R. Hill/Journul ofNon-Crysrulline Solids 196 (1996) 346-351 349

Table 1
Thermal analysis data for the (2 - x)SiO, . xP,O, . Al,O, . CaO . yCaF, glasses studied
Series x Y Ca:P Tg, (“Cl Tg2 (“C) Tp, (“C) Tp2 (“C) T P3
A 0.00 1.00 642 707 876
A 0.25 1.00 4.00 631 713 172 834
A 0.50 1.oo 2.00 621 723 814
A 0.75 1.00 1.33 662 758 826 878 103
A 1.00 I .oo 1.00 669 751 818 860 101
B 0.50 1.oo 2.00 621 723 814
B 0.50 0.75 1.75 640 761 943
B 0.50 0.50 1.50 668 815 987
B 0.50 0.25 1.25 117 834 107
B 0.50 0 1.0 819 922 109

The estimated error on the DTA data is rt 3°C.

Indentation fracture toughness measurements were
performed on cast samples using the method and
formulae described by Anstis et al. [ 141. The Young’s
modulus was assumed to be 120 GPa.
3. Results
X-ray diffraction was used to confirm that the
glasses produced were completely amorphous. Fig. 2
is a typical DTA trace showing the glass transition
temperature, q, and first and second peak crystalli-
sation temperatures, Tr, and Tp2. The glass transition
temperatures and peak crystallisation temperatures
for the A series glasses are given in Table 1.
All these glasses were found to crystallise to
apatite and mullite except the glass with x = 0 con-
taining no phosphate which crystallised to fluorite
(CaF,) and anorthite (CaAl,Si,Oa) and the glass
with x = 1 which crystallised to apatite and an alu-
minium phosphate, berlinite. The glass with x= 0.5
had a Ca:P ratio of 2.0 close to the apatite stoichiom-
etry of 1.67 crystallised to a large volume fraction of
apatite and was the basis of the B series of glass
compositions in Table 1.
The DTA results for the B series of glasses are
also given in Table 1. The glass transition tempera-
ture falls significantly with the value of y from
8 19°C at y = 0 to 621°C at y = 1, which is consis-
tent with calcium disrupting the glass network to
form non-bridging oxygens and, in addition, fluorine
replacing bridging oxygens with non-bridging fluo-
rines. All these glasses exhibited two crystallisation
exotherms, except the glass with y = 0 containing no
fluorine, which exhibited one. X-ray powder diffrac-
tion showed the first crystallisation peak was always
FAP. Glasses with y > 0.5 crystallised to mullite
(2Si0,.3Al,O,) as the second phase, while glasses
with x < 0.5 crystallised largely to anorthite. The
glass with y = 0 crystallised to only anorthite. Acti-
vation energies for crystallisation were determined
on selected glasses by the Matusita technique 1131,
the results are given below in Table 2.
The activation energy for the crystallisation of the

Table 2
Activation energies for crystallization
x Y Q-p I Phase EJp, Phase Assumed n Assumed m
(M mol- ‘) (kJ mol- ‘)
0.0 1.0 391 Fluorite 634 Anorthite 3 3
0.5 1.0 512 FAP Mullite 3 3
0.5 0.75 332 FAP Mullite 3 3
0.5 0.5 720 FAP Mullite 4 3
350 A. Clij)brd, R. Hill/Journal
Table 3
Indentation fracture toughness values obtained for the glass with
x = 0.5 and y = 0.5
Heat KIC
treatment (MPa rn’,‘) E 5)
None 0.78 0.11
Nucleated 1.40 0.09
0.5 h at 923°C 1.96 0.05
I .O h at 923°C 3.37 0.21
SD, standard deviation.
fluorite is low compared to that for anorthite for the
glass with x = 0 and y = 1. Neither fluorine nor
calcium forms part the glass network, and crystallisa-
tion to fluorite will not involve breakage of the
strong aluminium-oxygen-silicon bonds of the glass
network, consequently, crystallisation of fluorite will
occur readily with a low activation energy.
The glass with y = 0.5 was readily castable and
was selected for a preliminary investigation of its
fracture toughness before and after ceramming treat-
ments. The fracture toughness of the glass was mea-
sured in the cast state, following the nucleation
treatment and with a nucleation treatment followed
by 0.5 and 1.0 h at 923°C corresponding to the
crystallisation of FAP but below the onset tempera-
ture for the crystallisation of mullite. The results
obtained are given in Table 3. The fracture toughness
increases significantly following the nucleation treat-
ment but increases dramatically following the crystal
growth hold.
The microstructure of the samples cerammed at
923°C differed in the length of the apatite needles
produced, with the longer heat treatment time giving
rise to a crystal with a higher length to diameter
aspect ratio.
4. Discussion
Early infrared spectrum results show an absence
of hydroxyl groups and this, coupled with the high
proportion of fluorine present, suggests that he ap-
atite phase is fluorapatite (FAP) in both the A and B
series. This was later confirmed via X-ray diffraction
analysis and specific heat treatments which showed
the apatite phase to be fluorapatite in all cases.
ofNon-Crystalline Solids 196 (1996) 346-351
From the results of series A, there was no obvious
influence of glass composition and calcium to phos-
phate ratio on either the crystallisation temperatures
or crystalline phase formed. Both phosphate and
fluorine are known to cause amorphous phase sepa-
ration in glasses, and all the glasses of the A series
underwent amorphous phase separation, either during
quenching, as evidenced by a second glass transition
temperature, Tg2, or on subsequent heat treatment
prior to crystallisation. It is likely that the composi-
tion of the phase separated phases is more important
than the initial glass composition as regards the
subsequent crystallisation behaviour.
The B series of glasses exhibited an increasing
tendency towards surface nucleation as y was de-
creased, evidenced by a shift in the peak crystallisa-
tion temperatures to higher temperatures with in-
creasing particle size. Glasses in the B series with
y = 1 and 0.75 exhibited no shift in their penk crys-
tallisation temperatures with particle size. All of the
B series glasses were found to undergo amorphous
phase separation prior to crystallisation. In the case
of the glasses with y = 1 and 0.75, this led to bulk
crystal nucleation. Is the thought that bulk crystal
nucleation is aided by the fact that the apatite formed
is fluorapatite and that the fluorine packs more read-
ily into the apatite lattice than either a hydroxyl
group or an oxygen atom [ 151.
The first peak crystallisation temperature, corre-
sponding to that of FAP, reduces as y is increased. It
was thought that the peak crystallisation temperature
might go through a minimum at the apatite stoi-
chiometry of 1.67, but there was no evidence of this.
It is thought that, since these compositions undergo
APS prior to crystallisation, the composition of the
glass phase after phase separation is more important
than the initial composition of the glass. Jana and
Hdeland [lo] and Wood and Hill [6,8] have demon-
strated that similar compositions undergo amorphous
phase separation to give a calcium phosphate rich
phase, which subsequently crystallises to FAP and an
aluminium silicon rich phase.
The phosphate-containin g glasses that crystallised
to FAP exhibited an activation energy for crystallisa-
tion that was very dependent on the composition of
the glass. The activation energies obtained for crys-
tallisation of the mullite phase were always very low,
and the activation energy plots were never very
 A. Clifford, R. Hill/Journal
linear. Subsequent combined DTA/TGA showed that
these glasses underwent a sharp weight loss accom-
panying the crystallisation of mullite. The weight
loss is due to the formation of volatile silicon te-
trafluoride from the silicon and fluorine rich glass
which is left after crystallisation of FAP and mullite.
The high fracture toughness results obtained are
thought to be due to the elongated nature of the FAF’
crystals and the fact that they undergo a pull-out
process during failure giving rise to a large work of
fracture.
5. Conclusions
Glasses with intermediate phosphate contents and
high fluorine contents bulk nucleated via prior amor-
phous phase separation. Both the fluorine and the
phosphate content of the glass are important in ob-
taining bulk nucleation of the FAP phase. The cal-
cium:phosphate ratio of the glass did not have a
significant influence on the peak crystallisation tem-
perature of the FAP phase. High fracture toughness
values, > 3.0 MPa rn’.‘, could be obtained for cer-
ammed materials with microstructures consisting of
FAP crystals with a high length to diameter aspect
ratio.
ofNon-Crystalline Solids 196 (1996) 346-351 351
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