HYDROXYAPATITE - CHITOSAN BIOCOMPOSITES

Maria Ratajska, K. Haberko*, Danuta Ciechańska,

Antoni Niekraszewicz, Magdalena Kucharska

Institute of Biopolymers and Chemical Fibres, Lodz, Poland

e-mail: ibwch@ibwch.lodz.pl

*AGH –University of Science and Technology, Kraków, Poland

1. Introduction
Bone repair or regeneration is a common and complicated clinical problem in orthopedic
surgery. Every year, millions of people are suffering from bone diseases arising from trau-
ma, tumour or bone fractures and unfortunately some of them are dying due to insufficient
of ideal bone substitute [1]. Metallic implants are widely used in many treatments and are
fairly successful. However, they do not provide the optimum therapy due to their shortcom-
ings such as stress shielding during post-healing, chronic inflammation caused by corrosion,
and fatigue and loosening of implant [2]. As a result a second surgery is often required to
remove the metallic implant. Even though authogenic bone performs better functions in
terms of biocompatibility and other factors, it also needs secondary surgery to procure do-
nor bone from the patient‘s own body. A desirable material for use in clinical orthopedics
is a biodegradable biomimetic material that induces and promotes new bone formation by
osteogenic cells at a required site. Ideally, these materials should be in form of scaffolds,
which provide space for tissue development and offer temporary mechanical support [3, 4].
Potentially suitable biomaterials for use in bone tissue engineering include ceramics (e.g.
hydroxyapatite (HAp)) and polymer. In presented paper as a polymer chitosan (Ch) was
used. Chitosan is a biocopolymer comprising of glucosamine and N-acetyloglucosamine,
obtained by deacetylation of chitin.

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 M. Ratajska, K. Haberko, D. Ciechańska, A. Niekraszewicz, M. Kucharska

The aim of the paper was to elaborate a new, modern group of the products which could
be used as an adhesive or implants in orthopedic surgery. The optimum composition and a
method of production should be found.

2. Materials and methods

HAp powder was extracted from the cortical part of long pig bones. Two kinds of HAp were
studied: After standard technique of preparation [5], the material was heated at the tempera-
ture 450 and 700 °C. The properties of the formed powders were studied using standard
analytical methods: FTIR, DTA. TG, X-ray diffraction.

Chemical analysis of both samples is comparable, and gives following results:

Powder heated at 400 °C: CaO – 51.91%; P2O5 – 38.25%; MgO – 0.60%; Na2O – 2.84%.
Powder heated at 700 °C: CaO – 52.30%; P2O5 – 38.66%; MgO – 0.59%; Na2O – 2.06%.

Other parameters of both samples are very similar. As an example in Figure 1 an X-ray dif-
fraction pattern of one kind of HAp is shown.

The other HAp sample gives identical result. The size of crystallites counted with half
breath of (002) reflex is: a = b = 9.388 Å, c = 6.8863 Å.

In Figure 2 is given SEM photo of of HAp sample heated at 700 °C. In the figure can also
be seen a distribution of grain size. Grain size fits mainly in the range 0.2 – 0.4 µm. The
individual grains of higher size form probably agglomera

Figure 1. X-Ray diffraction pattern of the HAp calcinated at 700 °C.

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 Hydroxyapatite - chiosan biocomposites

Three kinds of initial chitosan were studied. Their properties are compared in Table 1.

Above characterized chitosans were used to produce their’s useful forms:

- Microcrystaline chitosan [6]
- Salts of chtosans
- Salts of chitosans with increased pH.

Chitosan was mixed with HAp in different weight proportions. As an example FTIR spectra
of composites with HAp heated at 700 °C are shown in Figure 3.

As it can be observed both chitosan and HAp characteristic absorption bands can be ob-
served. Their intensity is proportional to the component amount in the mixture.

3. Results and discussion

HAp/chitosan composites were used to produce their useful, 3-dimencial forms. The best
results were received for the compositions collected in Table 2.

Figure 2. SEM micrograph of HAp 700 powder and its grain size distribution.

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 M. Ratajska, K. Haberko, D. Ciechańska, A. Niekraszewicz, M. Kucharska

Table 1. Some properties of initial chitosan.

Content of
Sample Mv, kD SD, % heavy metals, Ash content, % WRV, %
%
Chitosan 1
Vanson 401.0 79.6 0.07 1.30 244.0
01-ASSC-1604
Chitosan 2
Vanson 344.0 81.7 - 0.14 100.0
03- CISB - 0278

Chitosan 3
346.0 82.2 0.02 0.28 291.0
Primex FG 90

Table 2. Composition of 3-dimentional forms of HAp/MKCh.

MKCh properties
Composition Composit’s WRV,
Sample
HAp : MKCh %
Mv, kD SD, %

HAp / MKCh-10 50 : 50 169

HAp / MKCh-11 10 : 90 280

HAp / MKCh-12 307.0 81.7 25 : 75 197

HAp / MKCh-14 75 : 25 109

MKCh - refrence 100 134

2,5
HAp 700 oC

chit 100% HAp:chit=1:9 HAp:chit=2:8 HAp:chit=3:7

A 2 HAp:chit=4:6 HAp:chit=5:5 HAp:chit=6:4 HAp:chit=7:3
b HAp:chit=8:2 HAp:chit=9:1 HAp 100%
s
o 1,5
r
b
a 1
n
c
e 0,5

0
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers, cm -1

Figure 3. FTIR spectra of HAp/chitosan mixtures.

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 Hydroxyapatite - chiosan biocomposites

In Figure 4. are given the chosen photos of sponges made of HAp / MKCh composites.

MKCh - reference HAp/ MKCh-12 (25:75) HAp/ MKCh-14 (75:25)

Figure 4. HAp/ MKCh sponges.

The compositions HAp/ MKCh form well shaped 3-dimensional structures which can be
used in future as a base for scaffolds production. Crystals of HAp form aggregates well
seen in cross section of sponges.

Similar 3-dimentional structures can be formed using chitosan lactate instead of MKCh as a
component of the mixture. Photos of such structures are given in Figure 5.

HAp400/ML 1/0.5 HAp 400/ML 1/1 HAp 400/ML 2/1

HAp700/ML 1/0.5 HAp 700/ML 1/1 HAp 700/ML 2/1

Figure 5. HAp/chitosan lactate sponges.

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 M. Ratajska, K. Haberko, D. Ciechańska, A. Niekraszewicz, M. Kucharska

4. Conclusions
1. Both samples of HAp form with chitosan and it’s useful forms (MKCh, chitosan lactate)
well shaped 3-dimentional forms – sponges.
2. The sponges can be used as implants in orthopedic surgery
3. 3-dimentional structures of HAp/chitosan composites are a good base for scaffolds pro-
ductin.

5. Acknowledgment
The studies realized within the research project No 3 T98E 037 29, supported by the Ministry of
Science and Higher Education

6. References
1. Murugan R., Ramakrishna S.: “Bioresorbable composite bone paste using polysaccharide based
nano hydroxiapatite”. Biomaterials 25 (2004) pp. 3829-3835.
2. Qiaoling Hu and others: “Preparation and characterization of biodegradable chitosan/ hydroxy-
apatite nanocomposite rods via in situ hybridization: a potential material as internal fixation of
bone fracture”. Biomaterials 25 (2004) pp. 779-785.
3. Feng Zhao and others: “Preparation and histological evaluation of biomimetic three-dimensional
hydroxyapatite/chitosan-gelation network composite scaffolds”. Biomaterials 23 (2002) pp. 3227-
3234.
4. Marciniak J.: Biomateriały, Wydawnictwo. Politechniki Śląskiej, Gliwice 2002.
5. Haberko K. and others: „Natural hydroxyapatite – its behaviour during heat treatment”. Journal
of the European Ceramic Sociaty 26 (2006) pp. 537-542
6. Struszczyk H.: “Progress on the Modification of Chitosan, Advances of Chitin Science” vol. II
Lyon, France, 1996 pp. 245 – 253.

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