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Biomaterials 24 (2003) 255\u2013262
Compactibility study of calcium phosphate biomaterials
C. Nicolazoa, H. Gautierb,c,*, M.-J. Brandaoc, G. Daculsic, C. Merleb,c
aLaboratoire de M!
ecanique des Solides et des Mat!
eriaux FORSEM, Institut Universitaire de Technologie de Nantes, 3 rue du Mar!
echal Joffre,
BP 34103, 44041 Nantes Cedex 1, France
e de Pharmacie, Laboratoire de Pharmacie Gal!
enique, 1 rue Gaston Veil, 44035 Nantes Cedex, France
cCentre de Recherche sur les Mat!
eriaux D\u2019int!
et Biologique, Equipe Mixte INSERM 99-03, Facult!
e de Chirurgie Dentaire, 1 place Alexis Ricordeau,
44042 Nantes Cedex, France
Received 22 January 2002; accepted 23 July 2002

This study investigated the micromechanism responsible for the densi\ufb01cation and consolidation of powders during dynamic compaction, an experimental process in which ceramic is formed without heating. Three calcium-de\ufb01cient apatites (CDA: two powders and a \ufb01brous compound) and a biphasic calcium phosphate (BCP) were studied to determine their aptitude (rheological and physical properties) for compactibility under various dynamic compaction pressures. Powders were investigated for their physicochemistry, particle size, and \ufb02ow time, and compacts for their compaction rate, density, speci\ufb01c area, mechanical characteristics, and disintegration time. Powder particles showed different morphological features depending on the synthesis protocol used, speci\ufb01c area and rheological behaviour. Compacts were not obtained with BCP, regardless of the gas pressure used, whereas CDA produced compacts with good mechanical properties (high hardness and compression stress), particularly for the \ufb01brous compound. The poor compressibility and compactibility of BCP powders were con\ufb01rmed, whereas \ufb01brous CDA powders showed good compactibility conducive to high-quality \ufb01lling of biomaterials.

r2002 Elsevier Science Ltd. All rights reserved.
Keywords:Dynamic compaction; Apatite; Biphasic calcium phosphate; Compactibility; Rheology
1. Introduction

The treatment of various pathologies in orthopaedic and dental surgery requires the implantation of a biomaterial to compensate for bone loss due to trauma and fracture and promote healing. The use of these substitutes has developed within recent decades, and calcium phosphate biomaterials [1] have now largely replaced calcium sulphate [2,3]. As the chemical composition of calcium phosphate biomaterials is similar to that of vertebrate mineral phases (bone, dentin, etc.) [4,5], they have proved to be ef\ufb01cient bone substitutes. Calcium-de\ufb01cient apatite (CDA), hydroxy- apatite (HA) andb-tricalcium phosphate are frequently used [6,7], either alone or in association, e.g. biphasic calcium phosphate (BCP) [8,9].

These calcium phosphate biomaterials are prepared in powder, granule or block form. In the case of ceramic powders, the preparation of implants with a shape adapted to the bone defect includes a cold compaction stage followed by sintering. The latter can be replaced by dynamic compaction, a new process without heating (University of Nantes, Patent No. 92-12837). The technique involved is similar to that used for the preparation of metallic materials [10]. Densi\ufb01cation results from the impact of a projectile, which produces a compression wave that propagates in the powder. The wave deforms powder particles so rapidly that they amalgamate without any need for heat treatment [11]. Compacts obtained can be cut to prepare small blocks of various sizes, or granulated to prepare granular form of biomaterials, or mixed with hydroxypropylmethyl- cellulose to prepare injectable bone substitute in order to \ufb01ll up osseous defects [9].

Previous studies considered the advantages of dy- namic compaction for preparing calcium phosphate biomaterials [11] or loading them with human growth

*Corresponding author. Facult!
e de Pharmacie, Laboratoire de
Pharmacie Gal!
enique, 1 rue Gaston Veil, 44035 Nantes Cedex, France.
E-mail address:helene.gautier@sante.univ-nantes.fr (H. Gautier).
0142-9612/02/$ - see front matterr 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 6 1 2 ( 0 2 ) 0 0 3 1 3 - 7

hormone and vancomycin [12,13]. A previous report suggested that BCP has poor compactibility properties [14]. The present in vitro study investigated the micromechanism controlling the densi\ufb01cation and con- solidation of powders during the compaction process. Four types of calcium phosphate biomaterials synthe- sised in our laboratory (three CDA and a BCP) were studied to determine the one with the best mechanical properties after dynamic compaction. The physicochem- ical and rheological properties of the four powders were de\ufb01ned, as well as the mechanical properties of the resulting compacts.

2. Materials and methods
2.1. Synthesis of CDA

CDA powders were synthesised in the laboratory using a hydrolysis reaction. Three CDA (CDA 1, CDA 2 and \ufb01brous CDA) and a BCP were prepared from dibasic calcium phosphate dihydrate (DCPD) [15]. CDA 1 and \ufb01brous CDA were synthesised in ammoniacal solution during 4 and 12 h, respectively, and CDA 2 in sodium hydroxide solution during 4h. The powders obtained were puri\ufb01ed by washing and then oven-dried at 401C to a constant weight.

BCP powder was then obtained by sintering at 10501C for 420 min in a Vecstar furnace (Eurotherm, Switzerland). BCP powder was sieved using a Roto-Lab sieve (Chauvin, France) to collect the 0\u201340mm fraction.

2.2. Physicochemical characterisation, particle size and
rheological properties of powders
2.2.1. Physicochemical characterisation

X-ray diffraction pro\ufb01les of CDA and BCP powders were performed between 201 and 401 (2y) on a PW 1730 X-ray generator (Philips, France). Fourier transform infrared spectroscopy (FTIR) was performed on pow- ders using the KBr pellet technique (BCP/KBr: 1/300 mg). Infrared spectra were obtained on a Magna 500 FTIR spectrometer (Nicolet Inc., Paris, France) in the 400\u20134000 cm

2.2.2. Particle size

Powder morphology was studied by scanning electron microscopy (SEM) on a JSM 6300 (Jeol, Japan) coupled to a semi-automatic image analyser (Quantimet 500, Leica, UK) after gold\u2013palladium coating (Emscope AEI 230, Ashford, UK).

The speci\ufb01c area of CDA and BCP powders was measured according to the Brunnauer Emmet Teller (BET) method [16] on a Micromeritics apparatus (ASAP 2010, France). Results are expressed as the mean (m2g

\u00c01)7SD of three measurements.

Laser diffraction was used to analyse particle size on a Coulter LS 230 apparatus (Coultronics, France). Three measurements were performed on each sample, and results are reported as mean diameter (mm) expressed in volume7SD.

2.2.3. Flow measurement

True density was determined with an Accupyc 1330 pyknometer (Micromeritics, France). Results are ex- pressed as the mean of ten measurements (g cm


Flow time was determined in accordance with European Pharmacopoeia [17], using 50g of each powder. Results are expressed as the time (s) necessary for powder to \ufb02ow out.

Powder tapping was determined in accordance with European Pharmacopoeia [17], using 50g of each powder in a tap-volume-meter. Tapping ability (ml) was calculated asV10\u00c0V500;corresponding to the volume after 10 and 500 tapping. Tapped density was calculated according to [18].

2.3. Dynamic compaction of powders
Dynamic compaction was performed in our labora-
tories (Centre de Recherche sur les Mat!
eriaux d\u2019Int!

et Biologique, Nantes, France). The shock compaction apparatus was positioned horizontally to allow static precompaction of the powder before \ufb01ring. The powder (3.2 g for CDA powders and 8 g for BCP powder) was precompacted uniaxially in a 20-mm-diameter cylind- rical die using a power press (25-ton Power Team, SPX Corporation, USA) with 1 MPa pressure for 1 min.

The Hopkinson bar apparatus \ufb01red a 20-mm- diameter, 150-mm-long projectile into the same die used for static precompaction. Powders were compressed with a gas pressure of 0.5, 0.7 or 0.9 MPa, correspond- ing, respectively, to a projectile velocity of 31, 39 and 47 m s

\u00c01. Four compacts were obtained for each gas
2.4. Compact characterisation
2.4.1. Compaction rate, density and speci\ufb01c area
The compaction rate for each compact was calculated
using the following equation:
Compaction rate\u00bc \u00f0Vi\u00c0Vf\u00de=\u00f0Vi\u00c0Vtrue\u00de;

whereVi is the apparent initial powder volume (powder mass/tapped powder density),Vfthe compact volume, andVtruethe true powder volume (powder mass/true powder density). Thus, a 100% compaction rate corresponds to a compact without porosity, and a 0% rate to no compaction. Results are expressed as the mean of four measurements (%)7SD.

Apparent densities were calculated for precompacts
(after static precompaction) and for compacts (after
C. Nicolazo et al. / Biomaterials 24 (2003) 255\u2013262
dynamic compaction). Results are expressed as the mean
of four measurements (gm
\u00c03)7SD (for apparent
compact density).

The speci\ufb01c area was measured using the BET method described above. Results are expressed as the mean of three measurements (m2g

2.4.2. Mechanical characteristics

The non-destructive hardness test was performed on each sample (four samples for each gas pressure and powder). Two samples were then used to measure compressive strength and two to measure tensile strength.

Hardness (HV), as measured by the Vickers indenta- tion method, consists on sticking under a constant load, a square base pyramid of 1361 vertex angle, in the sample. HV was the ratio of the load by the impression surface let into the sample by the pyramid. HV was determined on a microhardness machine (Micromet 2100 Series; Buelher, France) using an indenting load of 1N. Results are expressed as the mean of four measurements7SD.

Maximum tensile strength (Rt) was determined by a
diametral compression test [19]:

whereP is the applied load (N),D the specimen diameter (mm), ande the specimen thickness (mm). Results are expressed in MPa.

Maximum compressive strength (Rc) was determined by an axial compression test using a Testwell-type machine (Wolpert, Germany). A force was applied parallel to the axis of the compact at a crosshead speed of 0.8 mm min

\u00c01. Compressive strength was calculated
from the load\u2013time curve by dividing the failure load by
the compact area. Results are expressed in MPa.
2.4.3. Disintegration test

A disintegration test was performed in water at 371C in accordance with European Pharmacopoeia [17], using a dilutest Pharma Ptz Test with a sample of each compact and precompact.

3. Results
3.1. Physicochemical characterisation, particle size, and
rheological properties of powders
3.1.1. Physicochemical characterisation

X-ray diffraction pro\ufb01les of CDA performed after sintering showed peaks corresponding to the two phases (HA andb-TCP) to be clearly identi\ufb01ed [20].

CDA 1 and \ufb01brous CDA showed a spectrum identical
to that of BCP. The HA/b-TCP ratio of these powders
was 65/35, corresponding to a mean calcium phosphate
ratio of 1.61.

CDA 2 after sintering gave a 100% TCP powder, corresponding to a mean calcium phosphate ratio of TCP (1.5).

FTIR of BCP powder showed typical peaks [5]. CDA 1 and \ufb01brous CDA showed identical peaks, and the CDA 2 spectrum was typical of TCP spectra. No calcium pyrophosphates were detected.

3.1.2. Morphology, speci\ufb01c area and particle size
SEM photographs of the four powders are shown in
Fig. 1.

SEM surface analysis of BCP powder indicated that this powder was composed of small particle agglomer- ates. The CDA 1 sample showed rough spherical granules. CDA 2 granules were angular, with numerous asperities. Fibrous CDA was composed of granules and \ufb01bres, and the granule surface was more regular than that of CDA 2, with few \ufb01bres on the surface.

Table 1 shows the speci\ufb01c area of CDA 1, CDA 2, \ufb01brous CDA and BCP powders. CDA 1 and \ufb01brous CDA, synthesised in ammoniac solution, had similar high speci\ufb01c areas (approximately 156 m2g

\u00c01), whereas
CDA 2 had a low surface area (17.2770.04 m2g
Sintered BCP had a very low surface area
(2.8570.01 m2g

The mean particle diameters of the different calcium phosphate samples are given in Table 2. CDA 2 and \ufb01brous CDA had larger diameters (nearly 24.65mm) than CDA 1 and BCP (13.270.01 and 6.670.20mm, respectively). Fig. 2 shows that all the populations were monodispersed, unlike BCP powder which was poly- dispersed.

3.1.3. Rheological characterisation

Rheological characterisation determined the true density, \ufb02ow time, tapping ability, and tapped density of the powders (Table 3).

The true densities of CDA 1, CDA 2 and \ufb01brous
2.749 g cm
\u00c02), whereas that of BCP was greater

(3.11770.001 g cm\u00c02). The same was true for tapped density. All \ufb02ow times were in\ufb01nite. BCP tapping ability was lower (16 versus 31.44 ml).

3.2. Compact characterisation
As BCP powder produced no solid compacts, it was
impossible to perform mechanical characterisation tests.
3.2.1. Compaction rate, densities and speci\ufb01c area

Table 4 indicates the precompact density, compaction rate, and densities and speci\ufb01c area of compacts for various gas pressures. The compaction rate and compact

C. Nicolazo et al. / Biomaterials 24 (2003) 255\u2013262

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