Journal of Dental Research

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Setting Reaction and Hardening of an Apatitic Calcium Phosphate Cement

M.P. Ginebra, E. Fernández, E.A.P. De Maeyer, R.M.H. Verbeeck, M.G. Boltong, J. Ginebra, F.C.M. Driessens and
J.A. Planell
J DENT RES 1997 76: 905
DOI: 10.1177/00220345970760041201

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J Dent Res 76(4): 905-912, April, 1997
Setting Reaction and Hardening
of an Apatitic Calcium Phosphate Cement
M.P. Ginebra*, E. Fernandez, E.A.P. De Maeyerl 2, R.M.H. Verbeeckl, M.G. Boltong, J. Ginebra3, F.C.M.
Driessens, and J.A. Planell
Departments of Materials Science and Metallurgy and 3Statistics and Operations Research, ETSEIB, Universitat Politecnica de Catalunya, Av.
Diagonal 647, 08028 Barcelona, Spain; lDepartment of Dental Materials Science, University Hospital, University Ghent, De Pintelaan 185, B-
9000 Ghent, Belgium; 2Senior Research Assistant of the N.F.S.R. (Belgium); *to whom correspondence should be addressed
Abstract. The combination of self-setting and
biocompatibility makes calcium phosphate cements
potentially useful materials for a variety of dental
applications. The objective of this study was to investigate
the setting and hardening mechanisms of a cement-type
reaction leading to the formation of calcium-deficient
hydroxyapatite at low temperature. Reactants used were at-
tricalcium phosphate containing 17 wt% 1-tricalcium
phosphate, and 2 wt% of precipitated hydroxyapatite as
solid phase and an aqueous solution 2.5 wt% of disodium
hydrogen phosphate as liquid phase. The transformation of
the mixture was stopped at selected times by a freeze-
drying technique, so that the cement properties at various
stages could be studied by means of x-ray diffraction,
infrared spectroscopy, and scanning electron microscopy.
Also, the compressive strength of the cement was measured
as a function of time. The results showed that: (1) the
cement setting was the result of the a-tricalcium phosphate
hydrolysis, giving as a product calcium-deficient
hydroxyapatite, while 1-tricalcium phosphate did not
participate in the reaction; (2) the extent of conversion of a-
TCP was nearly 80% after 24 hr; (3) both the extent of
conversion and the compressive strength increased initially
linearly with time, subsequently reaching a saturation level,
with a strong correlation observed between them, indicating
that the microstructural changes taking place as the setting
reaction proceeded were responsible for the mechanical
behavior of the cement; and (4) the microstructure of the set
cement consisted of clusters of big plates with radial or
parallel orientations in a matrix of small plate-like crystals.
Key words: apatitic cement, setting reaction, kinetics,
hardening, microstructure.
Received May 6,1996; Accepted October 3, 1996
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Introduction
Calcium phosphate cements have attracted much attention
in medicine and dentistry because of their excellent
biocompatibility and bone-replacing behavior, and their
ability to conform to the defects in hard tissues (tooth
structure, bone, etc.), which allows them to be placed close
to native bone. This is a result of their self-hardening
capability, which occurs through a setting reaction that
leads to the formation of a solid piece of precipitated
calcium phosphate at room or body temperature.
Today, several formulations of calcium phosphate
cements which result in hydroxyapatite are known (Monma
et al., 1984; Brown and Chow, 1986; Constanz et al., 1991).
Brown and Chow (1986) made a mixture of DCPD
(CaHPO4.2H20) or DCP (CaHPO4) with TTCP [Ca4(PO4)20]
in a molar ratio 1:1 and water or diluted aqueous solutions
of H3PO4. The reaction product was hydroxyapatite (HA),
CalO(PO4)6(OH)2, in both cases. Studies of the reaction
responsible for the setting of this cement have led to
improvement of its properties (Fukase et al., 1990; Ishikawa
et al., 1995a,b; Miyamoto et al., 1995).
With the same reactants used by Brown and Chow, it
was shown that it is possible to obtain calcium-deficient
hydroxyapatite (CDHA), Ca9(HPO4)(PO4)5OH, as the
reaction product, provided the reactants (TTCP with either
DCP or DCPD) are adjusted in a molar ratio 2:1 (Brown and
Fulmer, 1991). This fact is interesting, since CDHA seems to
be compositionally closer to bone mineral than
stoichiometric hydroxyapatite (Driessens and Verbeeck,
1990). By means of calorimetric studies and microstructural
observations, Brown and Fulmer determined the influence
of temperature on the kinetics of CDHA formation. They
observed that the reaction is not complete, since the
presence of reactants was detected even when the reaction
did not seem to proceed further.
The possibility that calcium-deficient hydroxyapatite
could be obtained from the hydrolysis of ot-tricalcium
phosphate (a-TCP), Ca3(PO4)2 between 60 and 100°C was
described by Monma and Kanazawa (1976). Subsequently,
they studied the effects of various additives on the ot-TCP
hydrolysis at 37 to 40°C (Monma et al., 1984). The main
905
906 Ginebra et al.
20 25 30
20
Figure 1. Diffraction patterns of the cement after immersion in
Ringer's solution at 37°C during t =0, 1,4, 16, 64, and 360 hrs.
products obtained were DCPD for pH < 5.5, octacalcium
phosphate (OCP), Ca8(HPO4)2(P04)4.5H20 in the range 5.5 <
pH < 7.5, and HA for pH > 7.5. The setting times varied
between 4 and 24 min; some additives acted as reaction
accelerators and others as retarders. However, they found
that the rate of hydrolysis was steeply reduced beyond pH
7.0 to 7.5, making it difficult for CDHA to be obtained at
physiological conditions.
In a previous paper, we have described a cement
formulation based on the hydrolysis of cx-TCP, resulting in
CDHA as the reaction product (Driessens et al., 1993). In the
meantime, this cement has been optimized with its
combined properties as a function of the working variables,
so that it now complies with all short-term clinical
requirements which play a role in bone surgery,
orthopedics, and dentistry (Ginebra et al., 1994). In contrast
to the results of Monma, it is observed that, at 37°C, the
transformation of df-TCP into CDHA can be completed
within a clinically acceptable period of time.
The suitability of this cement as a tooth replacement
material, with applications in alveolar bone maintenance,
has been evaluated recently (Jansen et al., 1995). After
implantation ofthe cement into artificial bone cavities in
goat tibia, histological evaluation reveals that the presence
of the cement stimulates the ingrowth of bone compared
with unfilled cavities. Active resorption and remodeling of
cement particles have been observed.
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J Dent Res 76(4) 1997
3000
2000
U)
)
10001-
nI
u-
-
I I
, I I I
0 100 200 300 400
t (h)
Figure 2. Intensity of some a-TCP, 13-TCP, and CDHA peaks as a
function of the reaction time of the cement.
The objective of this work was to investigate the kinetics
and mechanisms of the setting reaction of this cement. This
was done by stopping the transformation at selected times
to study the cement properties at various stages by means
of x-ray diffraction (XRD) and infrared spectroscopy (IR),
and to carry out microscopic observations on the
35 morphological evolution of the cement. The compressive
strength of the cement was measured as a function of time
of immersion in Ringer's solution at 37°C so that the
mechanical properties of the cement could be correlated
with the extent of conversion and the microstructural
changes during the transformation.
Materials and methods
Materials
We obtained the calcium phosphate cement used in this study
by mixing a powder and a liquid. The powder consisted of a
mixture of a-tricalcium phospate, [a-TCP or a-Ca3(PO4)21, with 2
wt% precipitated hydroxyapatite (PHA, Merck, Darmstadt;
catalogue number 2143). We prepared the ox-TCP by heating an
appropriate mixture of CaCO3 (Merck, catalogue number 2076)
and CaHPO4 (Merck, catalogue number 1.02144) for 15 hr at
1300°C, after which it was quenched in air. Since the stable phase
below 1180°C is its allotropic p-form, the monoclinic a-TCP can
become contaminated with some B-TCP when quenching is not
fast enough or when the components contain impurities which
promote the nucleation of 1-TCP. This explains why the a-TCP
contained about 15% B-TCP (Fema'ndez et al., 1995). The ca-TCP
was milled for 1 hr in an agate ball mill, the final powder having
a specific surface of (1.00 ± 0.03) m2/g.
The cement liquid was a 2.5 wt% solution of Na2HPO4
(Merck, catalogue number 1.06586) in water. The
liquid/powder ratio used was 0.32 mL/g.
Methods
Powder and liquid were mixed in a mortar for about 1 min. The
J Dent Res 76(4) 1997 Apatitic Cement: Setting Reaction and Hardening 907

12l00 I I I Table 1. Selected peaks for oa-TCP, ,B-TCP, and apatite (JCPDS
cards: ot-TCP, 29-359; f8-TCP, 9-169; apatite, 9-432)
1000
'64 -360h
Phase 20 ( h 1/1100
800
12.10 131,031 39
g600 16h 14.02 201 15
a-TCP 15.16 132 11
-° 400 22.20 201 24
24.10 161,331 33
200 30.74 034,434 100
0 2h ,B-TCP 27.80 214 55
a
31.02 2 0 10,2 1 7 100
0,0 0,1 0,2 0,3
displacement (mm) apatite 49.44 213 40
Figure 3. Load-displacement curves for a compression test of the
cement after immersion in Ringer's solution at 37°C during 1, 2, 4,
8, 16, 32, 64, and 360 hrs. in which w and M are the weight fractions and the mass
absorption coefficients, respectively. In this case, phases 1, 2, and
paste was used to fill cylindrical holes in a Teflon mold which 3 were a-TCP,,-TCP, and apatite, respectively. The values of the
had a diameter of 10 mm and a height of 5 mm. After 15 min, mass absorption coefficients were calculated to be (Cullity, 1978):
the samples were demolded and immersed in Ringer's solution
at 37°C for either 15 or 30 min or 1, 2, 4, 8, 16, 32, 64, or 360 hrs M1= M2 = 86.43 cm2/g (2)
(15 days) from the mixing of powder and liquid. For each
period, 6 samples were prepared. M3 = 84.97 cm2/g (3)
After removal of the samples from the Ringer's solution,
they were frozen in liquid nitrogen to stop the reaction. Water Since pure a-TCP could not be obtained, the calculation of w1 with
was then removed by freeze-drying in a lyophilizer type the use of a-TCP peaks was performed using the ot-TCP/0-TCP
ALPHA 1-4 connected to a control unit LDC-1 (Martin Christ mixture with known composition as a standard. For this mixture,
GmbH) for 15 hrs to prevent further reaction. Subsequently, 4 eq. (1) can be written as
samples for each series were crushed and then investigated with
x-ray diffraction (XRD) and infrared spectroscopy (IR). The l,initial Mlwl,initial (4)
remaining two samples were not crushed but were fractured so Il,o Wl,initiaiM, + (1 - wl,initiadM2
that the microstructure could be investigated with scanning
electron microscopy (SEM). with wnlitial the weight fraction of cx-TCP in the a-TCP/P-TCP
mixture and I iiitial the intensity of the a-TCP peak hkl in the same
mixture. The combination of equations (1), (2), and (4) then yields:
X-ray diffraction
X-ray diffraction patterns were recorded by step-scanning in a I, = M1w1 (5)
microprocessor-controlled diffractometer system (Philips PW- Il,initial wl,initial(Ml M3)(wl + w2) + M3J
-

1830). Ni-filtered Cu Ka radiation was used, with a PW-1836

automatic divergence slit and a graphite monochromator. The where IlO is eliminated and where the ax-TCP/,B-TCP mixture is
step-scanning was performed with an integration time of 10 sec the external standard.
at intervals of 0.020 (20). Heights of selected peaks were taken as a direct measure of
Indexing of the peaks was carried out by means of cards- the peak intensities, assuming a constant height/area ratio. The
JCPDS-29-359 for a-TCP, JCPDS-9-169 for 1-TCP, and JCPDS-9- standard deviation on the peak height was considered equal to
432 for apatite (Joint Committee on Powder Diffraction the square root of the number of counts.
Standards, 1988). If wo is wi at time 0 and w. is wi at time -, when no further
The relative amounts of the different phases present in the changes in the peak intensities are detected, the extent of
samples in each period of time were estimated on the basis of the conversion R at each time t (corresponding to wt) can be
peak intensity variation by means of the external standard method calculated from the general relation:
(Cullity, 1978). If Ij O is the intensity of a peak hkl for a pure
compound of phase j, and if Ij is the intensity of that same peak for R()=( - (wt - wOO)
o -w) w
a mixture of three phases 1, 2, and 3, it can be shown that R(%) = 100 (6)
- (wo W-)
Infrared spectroscopy
I Mjwj (1) Infrared spectra of the samples dispersed in CsBr tablets were
-j,o [wI(Ml - M3) + w2 (M2 - M3) + M3] recorded by means of a Mattson Galaxy 6030 Fourier Transform
Infrared Spectrophotometer.
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908 Ginebra et al. J Dent Res 76(4) 1997
Table 2. Weight fraction (w,) of ,B-TCP in the starting powder (t = 0) and after 360 hrs of reaction Results
Sample Phases Selected Peaks Intensity (cts)a
X-ray diffraction w _a
Pure 13-TCP ,-TCP 214 1 Fig. 1 shows the x-ray diffraction pattems
8856 ± 94
2 0 10,2 1 7 18894 ±137 1 of the powder obtained after different
t = 0 hr a-TCP + -TCP 214 1553 ±39 0.175 ± 0.006 hardening times. At t = 0, only peaks of
2 0 10,2 1 7 3474 ±60 0.184 ± 0.004 ox-TCP and ,B-TCP can be detected. As the
t = 360 hrs CDHA +1-TCP 214 1496 ±39 0.167±0.006 reaction proceeds, the a-TCP peak
2 0 10,2 1 7 3469 ±59 0.176 ± 0.004 intensities decrease and apatite peaks
appear and increase in intensity. At t =
a Mean ± SD (3 samples). 360 hr, the ox-TCP peaks disappear, and
apart from P-TCP peaks, only apatite
peaks are observed.
Scanning electron microscopy Quantitative analysis of the setting
reaction was performed with the peaks listed in Table 1.
Microstructures were investigated on gold-covered fracture They were selected on the basis of the following criteria:
surfaces by scanning electron microscopy in a JEOL 6400 (1) Relative intensity I/Ioo should be at least 10%, and (2)
microscope under 10 and 15 KV. the peaks should not overlap with other peaks. Fig. 2
gives the intensity of a representative peak of each of the
Compressive strength
Cylindrical samples of the cement were prepared with a Table 4. Infrared frequencies of vibrations observed in the
diameter of 6 mm and a height of 12 mm in Teflon molds. After hardened cement, after 360 hrs of reaction, compared with the
15 min, they were immersed in Ringer's solution at 37°C for frequencies reported in the literature for the CDHA
periods of 1, 2, 4, 8, 16, 32, 64, and 360 hr. For each period, 8
samples were prepared. After immersion, the samples were Frequency (cm'1) Frequency (cm-') Vibration
in the Cement CDHA according
polished, removed from the molds, and tested under
compression at a cross-head speed of 1 mm/min with an to Literaturea
Instron Universal Testing Machine type 4507.
3570 wb 3572 w OH stretching

Statistical analysis 3420 b 3400 water-adsorbed deformation

A statistical model was fitted by least squares for evaluation of
the time-dependence of both the extent of conversion and the 1640w 1625 OH water-adsorbed bending
compressive strength. A different model was used to 1215 sh,w 1210 BOH mode of HPOj2
determine the relation between compressive strength and the hydrogen-bonded
extent of conversion.
1135 sh,vw 1133 sh, w v3 vibration component
of HPO42- groups
1085 sh 1087 s V3 (PO4)
Table 3. Extent of conversion R according to the evolution of ar-TCP
weight fraction (wl) calculated from the XRD patterns by the -
1072 sh
extemal standard method (eq. 5) and variation of the compressive 1035 vs 1046 vs
strength of the cement as a function of the reaction time -
1032 sh
Time (hr) % Conversion (R) Compressive Strength (C), MPa 965 w 962 w v1 (PO4)
0 0 870 w 870 v5 P-O(H) deformation
1 6.9 (4.8)a 1.2 (0.04) of HPO42- groups
2 10.4 (4.5) 4.9 (0.2)
4 25.3 (2.6) 6.9 (0.5) 632 sh vw 630 m OH libration
8 55.6 (2.8) 20.3 (0.8)
16 72.8 (2.7) 29.1 (1.0)
24
605 m 601 m V4 (PO4)
- 32.7 (1.8)
32 83.8 (2.3) 36.2 (2.1)
64 89.8 (1.8) 39.4 (1-3)
565 m 571 m
360 100 37.9 (1.5) a
Berry, 1967; Fowler, 1974; Fowler et al., 1966.
b w = weak; s = strong; m = medium; sh = shoulder; b = broad;
a
Bracketed figures indicate SD of the mean. vw = very weak; vs = very strong
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j Dent Res 76(4) 1997 Apatitic Cement: Setting Reaction and Hardening
three phases as a function of
hardening time. It should be taken
into account that, in the beginning 100 -
of the setting, when apatite starts 90 -
to precipitate, the peak intensities
of this phase can be interpreted 80
only semi-quantitatively, because
the apatite crystals are probably 70
very small, which influences their 60
peak widths. Although the same
problem can hold for the a-TCP 50--
crystals for large reaction extents,
when only small a-TCP crystals 40 -
remain, the relative errors on these
large values of R(%) due to this 30 -
effect will be smaller. 20
From Fig. 2, it can be seen that
the 1-TCP peak intensity remains 10
constant within the limits of error.
This is confirmed by the values of 0e
the weight fraction of ,B-TCP at the
0 50
beginning (t = 0 hr) and at the end
(t = 360 hr) of the reaction,
calculated according to eq. (1) Figure 4. Extent of conversion R and compressive strength C of the cement as a function of the
with j = 2 by comparison with the reaction time. Each point represents the mean value of N=6 samples ± SD of the mean.
peak intensities for pure ,B-TCP,
with w1 + w2 = 1 when t = 0 hr and
wi = 0 when t = 360 hr. The presenc e of 2% PHA in the with C. (final compressive strength) = (39.8 ± 4.3) MPa and
starting powder was considered neg ligible. The results,
listed in Table 2, indicate that 0-TCP (does not participate
in the reaction and that the transfo:rmation consists of
the dissolution of ot-TCP and the precipitation of an
apatite phase.
The 6 ao-TCP peaks from Table 1 were used for the
calculation of w1 according to eq. (5), where w2 was
substituted by 0.175. The mean valLue w- was used to
calculate the extent of conversion R acciording to eq. (6). The
results are given in Table 3. A weig,hted least-squares
regression analysis demonstrates that R varies with time
according to eq. (7), with T = (13.7 +t 4.5) hr at the 95%
confidence level and a correlation coeffi cient r2 = 0.9199.
R(%) = (i -e ) 10( o (7)
Compressive strength
Typical load-displacement curve,s obtained in the
compression test are given in Fig. 3. As the reaction
proceeds, there is an increase in the cement strength as
well as a decrease in the plasticit) of the paste. The
compressive strength as a function of tiime is given in Table
3. A weighted least-squares re gression analysis
demonstrates that the compressive str,ength C varies with
time according to eq. (8)
C(t) =CC1 -eJ (8)
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909
60
50
-
40
-
30
300-.
9}
r%r
20
-
. I 0
I I
100 150 200 250 300 350 400
t (h)
T = (13.8 ± 3.8) hr at a 95% confidence level, and a
correlation coefficient r2 = 0.9763. The adequacy of
equations (7) and (8) for representing the experimental data
is illustrated in Fig. 4, which shows that the setting reaction
of the cement is correlated with an evolution in its
mechanical properties.
Infrared spectroscopy
In Fig. 5, the infrared spectra of the cement are given after
t = 0, 4, 16, and 360 hrs of reaction. The absorption
frequencies detected after 360 hrs of reaction are listed in
Table 4, together with those of CDHA, according to the
literature. In these spectra, the absorptions at 965 cm-1 (v1
of P04), at 1035 and 1085 cm-1 (V3 of P04), and at 565 and
605 cm-1 (V4 of P04), typical for apatite, become more
pronounced with increasing reaction time. However,
absorption bands at 3570 cm-1 and near 630 cm-1 of the
stretching and libration, respectively, of the OH-groups in
HA are barely detectable in the spectra, even at t = 360
hrs. This can be ascribed to the overlap with the water
band near 3420 cm-1 and with the v4-PO4 band,
respectively, and to the fact that the OH-sublattice of the
apatite is not fully occupied. Moreover, the absorption
bands near 865, 1135, and 1215 cm-1, which increase with
time, indicate that the reaction product of the cement is a
calcium-deficient hydroxyapatite with a composition
most probably close to that of Ca9(HPO4)(PO4)5OH,
taking into account that the Ca/P molar ratio of the
original a-TCP is 1.5.
Evolution of the microstructure
Some representative SEM pictures of fracture surfaces of the
910 Ginebra et al. j Dent Res 76(4) 1997
stages can still be distinguished, but the space
previously occupied by the a-TCP particles is
now occupied by the big laminar crystals. In the
last stage, for t > 64 hr, radial or parallel
orientations of the crystals occur with a more
compact aspect, probably due to crystal growth
(Fig. 60.

Discussion
XRD, IR, SEM, and compressive strength
deteminations gave complementary
information about the setting mechanism
and the transformation occurring during
T this setting: oa-TCP particles dissolve into the
r
a cement liquid, and CDHA crystals are
n formed by precipitation from that liquid.
a
m The stoichiometry of the transformation can
t be depicted as:
t
t 3 a-Ca3(I4)2 + H20 -* Ca9(HPO4)(P04)50H (9)
a
n
c This mechanism is quite different from that
S
of mixtures of monetite (CaHPO4) and
tetracalcium phosphate [Ca4(P04)20], when
mixed in a 2:1 ratio with the intention to
form CDHA. As shown by Brown et al.
(1991), the first step of the mechanism
consists of the reaction of half of the monetite
with the tetracalcium phosphate according to

ll65\ | 6CaHP04 + 6Ca4(P04)20 -+ 3Ca1O(P04)6(OH)2 (10)

after which the other half of the monetite
reacts with the hydroxyapatite according to:
6CaHP04 + 3Calo(P04)6(OH)2->
4Ca%(HPO4)(PO4)50H+ 2H20 (11)
3500 3000 2500 2000 1500 1000 500
Monma et al. (1984) obtained only a partial
Wavenumbers reaction of a-TCP and water in their
formulation. This may have been due to
Figure 5. Infrared spectra of the cement after immersion in RingEer's solution at 37°C insufficient milling of the a-TCP powders or
A
auring 4t = u,n) A±i,1140,ana
irrrin er horir;,,
%A arnu
CL .i.v~---l
nrs [transmLttance vs. Ihi
wavenumDer (cm-s)I. too short observation times. In our case,
both XRD and electron microscope
observations suggest a total reaction of the
cement at different reaction times are shown in Fig. 6. Four stages oa-TCP in less than 360 hrs.
can be distinguished in the evolution of the microstructure. In the With regarrd to the mechanism of crystal precipitation, it is
first stage, which runs up to 30 mn (Fig. 6a), the initial powder dear from the !micrographs that the CDHA crystals do not grow
exhibits a detached and sandy aspect. In the second stage, from directly on thEe reactant surface, but that there is a void between
30 min to 8 hrs (Figs. 6b and 6c), the smaller a-TCP particles have them and the oa-TCP particles, as can be seen, e.g., in Fig. 7c.
dissolved completely, whereas the bigger ones become Therefore, it c'ertainly is not an epitaxial growth simnilar to that
surrounded by a layer of small CDHA crystals, which can be reported in thEe case of CITP and DCP, where the apatite crystals
expected to retard the reaction. In the third stage, which runs grow epitaxiallly on the DCP particles (Brown and Fulmer, 1991),
from 8 to 64 hrs (Figs. 6d and 6e), the remaining a-TCP particles or to that whiich occurs during the setting of gypsum with the
keep dissolving but at a lower rate. Some laminar crystals of calcium sulfalte dihydrate crystals growing epitaxially on the
CDHA can be seen within the interstices, which are much bigger hemihydrate crystals J0rgensen and Posner, 1959).
than the first CDHA crystals precipitated. At the end of this stage, Both the extent of conversion and the compressive
particles of oa-TCP are hardly detected, but one can still see where strength of thwe cement initially increase drastically with time
they have been: The rims of small crystals formed in the first [Fig. 4; eqs. ('7) and (8)], subsequently reaching a saturation
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 Apatitic Cement: Setting Reaction and Hardening 911
j Dent Rcs 76(4) 1997

O- -
V .;'
1W I
Figure 6. SEM pictures of the cement after different times of reaction: (a) after 15 min; (b) after 1 hr; (c) after 4 hrs; (d) after 8 hrs; (e) aftcr 64
hrs; (f) after 360 hrs.

level. This decrease of the reaction rate as a function of time of our cement, as shown in Figs. 6(a) through (f), shows a
is correlated with the surrounding of the oc-TCP particles by strong resemblance to that of tricalcium silicate hydrolysis
layers of CDHA, as was indicated in the SEM pictures. This (Ginebra et al., 1995), in which the larger tricalcium silicate
kind of behavior is also observed in the hydrolysis of particles are surrounded by a dense layer of re-precipitate.
tricalcium silicate. In fact, the evolution of the microstructure Such a layer retards the further reaction (Brown, 1989).
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912 Ginebra et al.
X =D./:
i,20
15 -
15
10
10
0 10 20 30 40 50 60 70 80 90 100
R(%)
Figure 7. Compressive strength C of the cement as a function of the
extent of conversion R.
The fact that the values for T from eqs. (7) and (8) are the same
within experimental error suggests that C and R are correlated.
This is corroborated by a linear regression analysis, which
demonstrates that the relation between C and R is given by
C = CO + XR
with C0 = (-1.6 ± 1.6) MPa and X = (0.43 ± 0.02) MPa, with r2
= 0.9810. This linear model is shown in Fig. 7.
This strong correlation indicates that the microstructural
changes that are taking place as the reaction proceeds, e.g., the
entanglement of newly precipitated crystals, are responsible
for the mechanical behavior of the cement. This entanglement
can explain, for instance, the change in the plastic behavior of
the cement at reaction times < 4 hrs into a more brittle
behavior at t . 8 hrs (Fig. 3). As can be seen in Figs 6c and 6d,
new CDHA plates connect the a-TCP particles, which up to
that moment were detached, with the surrounding CDHA
crystals increasing the entanglement of the structure and
consequently the rigidity of the material. This fact illustrates a
possible method of modifying and improving, within certain
limits, the mechanical properties of these materials.
Acknowledgments
This investigation was supported in part by a grant from the
Direcci6n Cientifica y Tecnica of Spain. The authors thank
the CICYT for funding this work through project MAT94-
0911. Further, the authors are grateful to Ms. Marsal for her
assistance in making the SEM pictures.
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