Materials Chemistry and Physics 78 (2003) 816–824

A novel sol–gel technique for hydroxyapatite preparation

G. Bezzi a , G. Celotti b , E. Landi b,∗ , T.M.G. La Torretta a , I. Sopyan c , A. Tampieri b
a CRNM-ENEA, via Ravegnana 186, Faenza, Italy
b ISTEC-CNR, Institute of Science and Technology for Ceramics, via Granarolo 64, Faenza, Italy
c BPPT-Materials Technology Center, Jl. Mh. Thamrin 8, Jakarta, Indonesia

Received 19 July 2002; received in revised form 11 August 2002; accepted 12 August 2002

Abstract
The concept of biocompatible, osteoconductive material mimicking the structure of natural bone to be used as bone graft has generated
a considerable interest in recent decades. This paper reports on a novel and simple sol–gel technique for fabricating pure hydroxyapatite
powder. Compositional, microstructural, morphological and mechanical characterisations carried out on the powder as well as on dense
and porous sintered bodies, are also reported.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Biomaterial; Sol–gel process; Hydroxyapatite

1. Introduction phorus which is capable of improving the chemical homo-

When bone is lost due to injury and/or illness, the defects
are generally filled with natural bone because artificial bone
materials have the problem of bioaffinity. However, natural
bone also has supply and infection problems. Therefore,
studies are recently dedicated towards an artificial material
which has the same biological properties as bone and that
can replace natural bone for grafting.
In recent years, synthetic hydroxyapatite (HA) has as-
sumed substantial interest and importance because of its
chemical similarity to the natural Ca phosphate mineral
present in a biological hard tissue. Considering the numerous
applications of calcium phosphate compounds in biomedical
fields, numerous HA synthesis techniques have been devel-
oped. The most commonly used technique for the formation
of HA is the precipitation technique, involving wet chemical
reactions between the calcium and phosphate precursors un-
der controlled temperature and pH conditions [1–5]. How-
ever, this method has some inherent disadvantages, primarily
the difficult control of the pH value over 9 to avoid the for-
mation of a Ca-deficient HA which in sintering undergoes
to easy decomposition, forming tricalcium phosphates.
In this respect, the sol–gel technique is an elective method
for the preparation of highly pure powder due to the pos-
sibility of a strict control of the process parameters. This
method offers a molecular mixing of the calcium and phos-
∗ Corresponding author. Tel.: +39-0546-699-758; fax: +39-0546-46381.
E-mail address: elena@istec.cnr.it (E. Landi).
geneity. The sol–gel product is characterised by nano-size
dimension of the primary particles, and this small domain is
a very important parameter to improve the contact reaction
and the stability at the artificial/natural bone interface.
Moreover, the high reactivity of the sol–gel powder al-
lows a reduction of the processing temperature and of any
degradation phenomena occurring during sintering. The ma-
jor limitation to sol–gel technique application is linked to the
possible hydrolysis of phosphates and the high cost of the
raw materials [6]. Both problems are solved in the method
proposed in the present paper where a new process to pre-
pare a pure HA powder via the sol–gel route is presented.
2. Experimental
Wet chemical reactions to form calcium phosphate ma-
terials can be generally divided in two kinds of process in
terms of reagents concentration: non-homogeneous and ho-
mogeneous processes. In the first one, calcium phosphate
compound synthesis involves a dropwise adding of a donor
reagent of phosphorus into a calcium hydroxide or salt slurry.
In the second one, calcium and phosphorus salts (usually ni-
trate for calcium and ammonium phosphate for phosphorus)
are solubilised in water under a strict pH control. In both
cases a long ageing time is required to let the precipitation
reactions end, because it is very difficult during the precip-
itation phase to control that the single ion concentration is
uniform.

0254-0584/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 0 2 ) 0 0 3 9 2 - 9
 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824
The process described in this paper falls in the homoge-
neous category. Good reproducibility, high yield, simplicity
of execution, not use of solvent except water make this syn-
thesis very competitive related to other wet and sol–gel pro-
cesses and suitable for being scaled up to industrial size. A
very simple method was set up to obtain pure hydroxyapatite
[7]. Hydroxyapatite powder was prepared from calcium ni-
trate tetrahydrate (Aldrich) and ammonium hydrogen phos-
phate (Merck), adding etilendiamminetetraacetic acid (Carlo
Erba Reagenti) and urea (Merck) as gelling and ammonium
donor agents. To prevent an immediate precipitate formation
the calcium ions were chelated by etilendiamminetetraacetic
acid (EDTA) to permit a very good mixture with the phos-
phate ions. In this solution, under stirring, urea was solu-
bilised too. In this way the urea decomposition happens in a
very homogeneous system in terms of ion concentration and
pH. Nitrate ion removal involves a white gel phase formation
passing through a transparent sol phase in one reactor only,
to set at zero possible contamination. Pure HA powder was
finally obtained after a proper thermal cycle and a peculiar
chemical correction treatment, involving the hydrothermal
conversion of tricalcium phosphate (TCP) into HA.
The specific surface area of the powder was evaluated by
the Brunauer–Emmett–Teller method (Sorpty 1750, Carlo
Erba, Milano, Italy). For particle size distribution mea-
surement, the powder was analysed by sedimentography
(Sedigraph 5100, Micromeritics, Norcross, GA) after ultra-
sonic dispersion for 10 min. In order to evaluate Ca/P ratio,
inductively coupled plasma-optical emission spectrometry
(ICP-OES) analysis was performed (Liberty 200, Varian,
Clayton South, Australia). Fourier transformed infrared
(FTIR) spectroscopy (FT-IR 1750, Perkin-Elmer Instru-
ments, Shelton, CT, USA) was also performed in order to
follow the chemical evolution from the gel to the HA, and
to determine HA stoichiometry deviations, i.e. the presence
of anions partially substituting PO4 3− and/or OH− groups.
Simultaneous thermal analysis (Netzsch Geratebau STA
409) was used in order to follow the thermal transformation
process of the gel into HA and the hydroxyapatite thermal
stability.
The morphological evaluation of the powder and mi-
crostructural characterisation of the dense bodies was per-
formed by scanning electron microscopy (SEM; Stereoscan
360, Leica, Cambridge, UK). The powders as well as the
sintered bodies were also characterised by X-ray diffraction
(Cu K␣ radiation, Miniflex Rigaku, Tokyo, Japan) in order
to evaluate the crystalline phase compositions.
Zeta-potential determination was carried out with an elec-
troacoustic technique, using an electrokinetic sonic ampli-
tude (ESA) measurement apparatus (Acoustosizer, Colloidal
Dynamics, Sydney, Australia). The suspension sample was
prepared by ball milling the powder for 1 h into a 10−2 M
KCl solution to maintain a constant ionic strength. A fixed
concentration of 3 vol.% solid was used and the suspension,
placed in the measurement cell, was kept under constant
stirring at 25 ◦ C. The aqueous dispersing behaviour of the
817
HA powder was investigated through potentiometric titra-
tion. An automatic titration software was used to measure
the ζ potential and conductivity as a function of pH (HNO3
1 M and KOH 1 M were used to adjust the pH). The isolec-
tric point (IEP) was identified at the pH axis crossing point.
The HA densification behaviour was detected by thermal
dilatometry (Netzsch Geratebau E 402) in order to identify
the best sintering temperature. Dense samples were prepared
starting from a spray-dried HA powder. The flexural strength
was determined on suitable shaped bars (2 mm × 2.5 mm ×
25 mm) by a four-point bending device (Instron mod. 1195,
High Wycombe, Bucks, UK) with an outer span of 20 mm, an
inner span of 10 mm and a crosshead speed of 0.5 mm/min.
Porous samples were prepared by soaking natural cellu-
losic sponges (Spontex, Verniano, Italy) into 25 vol.% HA
suspension, containing Duramax D-3021 (Rohm and Haas,
USA) as a dispersing agent. The density of the porous bod-
ies was measured by geometrical weight/volume evaluation
(so-called apparent density).
The compressive strength of the HA porous bodies
was measured on cylindrical specimens 10 mm × 10 mm
(height × diameter) using an Instron machine mod. 1195
(High Wycombe, Bucks, UK) with a crosshead speed of
1.0 mm/min. To avoid a shear stress concentration, a thin
proper foil was inserted between each end of the cylinder
and the loading plates of the machine. The compressive
strength was calculated from the maximum load registered
during the test divided by the original area (six specimens
were tested).
3. Results and discussion
3.1. Sol–gel synthesis and powder characterisation
3.1.1. Method A
The flow sheet of the sol–gel process is shown in Fig. 1. To
produce about 100 g of pure hydroxyapatite powder (HAsg),
260 g of Ca(NO3 )2 ·4H2 O (98%), 79.7 g of (NH4 )2 HPO4
(99%), 360 g of EDTA and 90 g of urea are required, which
were solubilised in 1400 ml of distilled water containing am-
monia (7%), with a molar ratio Ca/P > 1.7. This solution
was heated at 90–120 ◦ C under stirring for about 2 h till wa-
ter evaporation and urea decomposition, passing through an
intermediate sol state, to obtain finally a white consistent
gel. This gel was slowly dried in air at 340 ◦ C, then fired
in air at 800 ◦ C for 2 h to obtain a white powder, which
was HA (main phase) together with about 14% ␤-TCP and
5% CaO (Fig. 2). The Ca/P ratio was corrected to 1.667
by adding a right amount of diammonium hydrogen phos-
phate to a water suspension of the powder and maintaining
the system under stirring at 90 ◦ C for ≈1 h. After drying at
120 ◦ C, the final pure hydroxyapatite powder was obtained,
as shown by X-ray diffractometry (XRD) analysis (Fig. 3).
The absence of Ca(OH)2 in the as-prepared powder was also
specifically controlled, analysing the powder after firing at
818 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824

Fig. 1. HA sol–gel synthesis flow sheet.

Fig. 2. XRD analysis of the powder obtained after the thermal treatment at 800 ◦ C.
 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824
Fig. 3. XRD analysis of the HAsg powder.
600 ◦ C: X-ray diffractometry did not evidence CaO forma-
tion; such a finding was also confirmed by the high precision
phenolphtalein test.
Fig. 4 shows the morphology of the synthesised powder:
even after the treatment at 800 ◦ C, the primary particles
resulted submicrometric in size, with a tendency to ag-
glomerate. Granulometric evaluation has been performed
on the as-prepared powder by X-ray sedimentography and
the mean particle size turned out to be ≈0.8 ␮m. Such a
value refers to the agglomerate dimension, surviving the
ultrasound treatment performed before the analysis, in or-
der to disaggregate the powder. The specific surface area,
evaluated by the Brunauer–Emmett–Teller method, was
7–11 m2 /g, which value is consistent with an average particle
Fig. 4. SEM image of the HAsg powder.
819
size about ten times lower than 0.8 ␮m, as well as shown in
Fig. 4.
To study the thermal transformation process of the gel, a
thermogravimetric analysis was performed on the gel using
a heating rate of 10 K/min. A total multistep weight loss of
≈80% was recorded (Fig. 5): the first drop at temperature
T ≈ 100 ◦ C is due to absorbed water, the second one starting
at T ≈ 200 ◦ C (≈50% of the total weight loss) can be
attributed to nitrates and urea decomposition, then at higher
temperatures the decomposition of acetates (from EDTA)
and hydroxides occurs (weight loss ≈ 25%). The DTA curve
is characterised by a sequence of peaks at T ≈ 300, 330
and 480 ◦ C, corresponding to the decomposition processes
of the compounds described above.
Such a behaviour is in accordance with the FTIR analy-
sis which was used to follow the evolution of the chemical
compounds contained in the initial gel up to the final HA
powder. In particular, the FTIR spectrum of the dried gel
Fig. 5. Thermogravimetric and differential thermal analysis (TG–DTA) of
the gel.
820 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824

Fig. 6. FTIR analysis of the gel after thermal treatment at 340 ◦ C.

(Fig. 6) yet shows broad peaks, typical of amorphous prod-
ucts, but anyway the characteristic bands of carboxylic and
carbonate (1400–1600 cm−1 ), phosphate (900–1100 cm−1 ),
amino (≈1400, 1600 and 3200 cm−1 ) and acetate (≈2800,
2300 cm−1 ) groups are still distinguishable.
The stoichiometric purity of the final powder in term of
chemical substitutions (CO3 2− and HPO4 2− can be present
as partially substituting groups of PO4 3− and/or OH− in the
HA structure) have been also controlled by means of ICP
and FTIR analysis.
The FTIR spectrum of the final powder shows the charac-
teristic peaks corresponding to OH− (630 and 3560 cm−1 )
and PO4 3− (960, 1050, 1090 cm−1 ) vibrations, together with
the weak bands of the CO3 2− group (870, 1415, 1450 and
very weak 1540 cm−1 ), which indicates that it is slightly
B-carbonated hydroxyapatite, as expected since the sol–gel
process involves organic reagents (Fig. 7). The ICP anal-
ysis performed on the final powder gave a Ca/P molar ra-
tio of 1.66, in accordance with the XRD evaluation (1.67),
considering the experimental errors. This value is also in

Fig. 7. FTIR analysis of the HAsg powder.

 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824
Fig. 8. XRD analysis of the HAsg powder after thermal treatment at 1250 ◦ C.
agreement with the FTIR analysis, keeping also into account
the opposite influence on the Ca/P value of the hydrogen
phosphate and carbonate ions as partially substituting groups
of PO4 3− in the HA structure.
To evaluate the thermal stability of the powder, XRD
analysis was performed after thermal treatment at 1250 ◦ C,
showing the absence of decomposition phases (Fig. 8). This
was in agreement with the result of a simultaneous thermal
analysis which detected no degradation phenomena of the
powder up to such a temperature.
3.1.2. Method B
The same procedure described in method A was applied
using a molar ratio of calcium nitrate and ammonium hy-
drogen phosphate to respect the HA theoretical Ca/P ratio
of 1.667. All attempts did not give good results, because
the final HA powder contained about 15 vol.% of TCP. The
process was then modified, starting with a higher value of
Ca/P ratio and correcting the excess by adding the phosphate
reagent during the gel formation. XRD showed that at the
end of the whole process, inclusive of the thermal treatment
of the gel, the main product was TCP (62 vol.%) together
with HA (38 vol.%).
In order to produce HA powder via a sol–gel route avoid-
ing the calcination at 800 ◦ C, the Ca/P ratio correction was
finally attempted on the product after the thermal treatment
at 340 ◦ C. Anyway, the XRD analysis on the calcined pow-
der pointed out the presence of 8–16% ␤-TCP as a secondary
phase. Also calcination pre-treatments and variations of the
cooling rate of the thermal cycle did not allow to obtain
pure HA powder as final product. On the basis of these re-
sults, the postponed Ca/P ratio correction was definitively
adopted, and the 100% pure HA powder produced and fully
characterised, as previously reported.
821
3.2. Characterisation of water suspensions of
HAsg powder
The isoelectric point of the HAsg powder dispersed in
H2 O was evaluated, by measuring the ζ potential versus
pH, in comparison with that of a powder (coded as pow-
der N) prepared by a classical precipitation technique via
the neutralisation route (powder N: specific surface area
35 m2 /g, 80% of crystallinity degree, molar Ca/P = 1.65
[8]). Being H+ , OH− and lattice ions the potential deter-
mining ions for apatite solids [9], the surface charge is the
result of pH and preferential dissolution or adsorption of
calcium and phosphate ions. The formation of surface com-
plexes between the potential determining ions further com-
plicates the estimation of the ion activity product and surface
potential.
The natural pH of the sol–gel and N powder suspension,
6.7 and 6.8, respectively, are higher than pH = 5.9 of the
surrounding medium solution (KCl 10−2 M, such a dispers-
ing medium is necessary to ensure a constant ionic strength
during the acid or base addition), as a consequence of the
HA basic hydrolysis in aqueous solutions, which is also in-
fluenced by the powder surface area. The ζ potential and
conductivity measurements as a function of pH are shown
in Fig. 9. The slightly negative ζ potential exhibited by the
sol–gel powder, at natural pH, is probably due to a prevailing
adsorption of HPO4 2− ions as regards to Ca2+ . The anionic
specific adsorption determines a shift of pHiep towards acid
pH. This shift is not evident for the powder prepared via
the neutralisation route, which shows a pHiep ≈ 7, close
to values reported in literature [10,11]. The suspension con-
ductivity showed a strong increase, which is attributed to
HA dissolution phenomena, at pH ≈ 4.5 and 6 for the HA
powder prepared via the sol–gel and neutralisation route,
822 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824

Fig. 9. Electroacoustic analysis of HAsg powder compared to HA powder prepared via classical neutralisation method.

respectively, indicating a lower solubility at pH close to neu- 3.4. Preparation and characterisation of dense
trality for the sol–gel HA. HAsg bodies

3.3. Preparation and characterisation of porous HAsg Considering that the optimal sintering temperature for HA
bodies powders depends on the starting powder features, and that
the lower temperature is defined by the excess in residual
A water-based slurry was prepared with 25 vol.% HA porosity at the grain boundaries and the higher one by the
powder and using Duramax D-3021 as dispersing agent at advancement of grain growth and of the degradation process,
the fixed concentration of 0.34 mg/m2 . Duramax D-3021 is sintering tests were performed.
a 40 wt.% solution of an ammonium salt of a polycarboxy- To prepare dense samples, HA powder was added with
late polyelectrolyte with a low molecular weight of approx- 5% polyvinylalcohol and spray-dried at 190 ◦ C. Fig. 11a
imately 2500 Da, pH = 7–8. shows the morphology of the spray-dried product formed
To prepare porous bodies, to be used as bone substitute, by spheric micrometric granules, which are constituted of
following the procedure elsewhere reported [12], cellulosic submicronic primary particles (50–200 nm, Fig. 11b).
sponges were soaked in the HA suspension and then dried at The shrinkage of cold isostatically pressed bars (100 MPa)
room temperature for 72 h. Finally, the porous samples were was recorded as a function of temperature by a Netzsch
thermally treated at 600 ◦ C for 1 h, using an heating rate of
50 K/h in flowing air to eliminate the organic matrix. The
sintering was performed at 1250 ◦ C for 1 h. The apparent
density of the porous bodies after sintering is 1.29 g/cm3 ,
with 59% of porosity. The linear sintering shrinkage was
about 20%.
The compressive strength was measured on cylindrical
specimens about 10 mm height × 10 mm diameter, using an
Instron machine 1195 with a crosshead speed of 1.0 mm/min.
The compressive strength value was 1.3 ± 0.3 MPa, which
is low in relation with the apparent density found, and in
comparison with previously reported data [12–14]. Even if
the slurry seemed to have a good fluidity, and it was kept in
an ultrasound bath during the soaking process, sedimentation
occurred giving rise to a disomogeneous impregnation of
the cellulosic matrix. Some big pores of the sponge were
completely filled with HA while the struts between them Fig. 10. SEM image of a portion of the porous sample: the original
appeared as scarcely loaded with HA, showing debris aspect porous structure of the sponge is lost; some macropores are completely
(Fig. 10). filled with HA and the struts between them show a debris aspect.
 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824 823

E402 dilatometer, using a heating rate of 5 K/min (Fig. 12).

The densification process starts at ≈1000 ◦ C and shows its
highest rate at about 1220–1250 ◦ C.
The flexural strength was determined on suitable shaped
bars (2 mm × 2.5 mm × 25 mm) by a four-point bending
device (Instron) with an outer span of 20 mm, an inner span
of 10 mm and a crosshead speed of 0.5 mm/min. The bars
were cut from a pellet, which was produced by cold press-
ing at 100 MPa the spray-dried powder, and then calcining
at 800 ◦ C (heating rate of 50 K/h) and finally sintering at
1250 ◦ C for 1 h (heating rate of 250 K/h). The sintering
temperature was chosen on the basis of the HA thermal
stability (beyond 1250 ◦ C the amount of ␣- and ␤-TCP
increases greatly over 2–3%). Two series of samples were
tested: (a) bars arising from uniaxially (100 Ma) pressed
powder and (b) bars arising from uniaxially (80 MPa)
and isostatically (100 MPa) pressed powder. The flexu-
ral strength resulted in 58 ± 7 MPa and 80 ± 10 MPa, in
agreement with the sintering density values 90 and 95%,
for samples (a) and (b), respectively. The SEM analysis
of the fracture surfaces sometimes evidenced macropores
(20 ␮m in size) or low-sintered areas together with micro-
porosity (1–2 ␮m in size), in the samples only uniaxially
pressed. The sintered surface of the isostatically pressed
samples (Fig. 13) showed limited intergranular porosity
together with a slight grain growth (grain size ≈ 2–5 ␮m).
X-ray diffractometric analysis pointed out that a nearly
undetectable amount (less than 1 vol.%) of decomposition
products formed in the sintered samples. The fracture anal-
ysis showed that the rupture was caused by the presence of
localised inhomogeneities in the microstructure (Fig. 14),
probably arising from the forming process, not yet well
Fig. 11. SEM image of the HAsg powder after spray drying treatment:
spheric micrometric granules (a) are constituted of submicronic primary
optimised.
particles (b).

Fig. 12. Thermal dilatometry of HAsg cold isostatically pressed sample, showing that the densification starts at about 1000 ◦ C, reaching the its highest
rate at 1220–1250 ◦ C.
824 G. Bezzi et al. / Materials Chemistry and Physics 78 (2003) 816–824
Fig. 13. SEM image of the fracture surface of a dense sample.
Fig. 14. SEM image of the microstructure inhomogeneity which caused
the fracture of a dense sample.
4. Conclusions
A novel and simple sol–gel synthesis of pure HA powder
was elaborated. Even if the process includes a thermal treat-
ment at 800 ◦ C, which reduces the potentiality arising from
nanometric powder, i.e. the reactivity in sintering, some pos-
itive results remain.
The uselessness of the control of temperature and pH
value during the synthesis and the absence of repeated fil-
tration and washing steps, which can easily cause loss of
material, are both important goals.
From the first tests the performance of the powder is
promising. The sintering temperature can be probably low-
ered also in function of an optimised pressing process, which
seems the most critical step.
Regarding the porous bodies production, a powder
pre-treatment and secondarily the determination of the sta-
bility conditions of the powder suspension seem inevitable
in order to prepare suitable slurries for the sponge impreg-
nation method.
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