IOP PUBLISHING BIOMEDICAL MATERIALS
Biomed. Mater. 3 (2008) 025014 (5pp) doi:10.1088/1748-6041/3/2/025014
Influence of hydroxyapatite crystallization
temperature and concentration on stress
transfer in wet-spun nanohydroxyapatite-
chitosan composite fibres
J Z Xie
1
, S Hein
2
, K Wang
3
, K Liao
3
and K L Goh
3
1
School of Engineering, Republic Polytechnic, Woodlands Ave 9, Singapore 738964
2
Interdisciplinary Nanoscience Center, Faculty of Science, University of Aarhus, Ny Munkegade,
Building 521, Aarhus C 8000, Denmark
3
School of Chemical and Biomedical Engineering, Nanyang Technological University, 637457
Singapore
E-mail: gohkl@ntu.edu.sg
Received 12 February 2008
Accepted for publication 15 April 2008
Published 14 May 2008
Online at stacks.iop.org/BMM/3/025014
Abstract
Hydroxyapatite possesses appropriate osteoconductivity and biocompatibility for hard-tissue
replacement implants but suffers from brittleness. One approach to overcome this problem is to
incorporate nanometre hydroxyapatite (nHA) into a polymer matrix, such as chitosan, to yield
a hydroxyapatite-chitosan (HC) composite. Here, a novel HC composite was synthesized and
its elastic properties were investigated by varying (1) nHA concentration and (2) crystallization
temperature (T), where T is a parameter which influences the morphology of the crystals.
Crystals of nHA were precipitated at T = 40
◦
C and 100
◦
C, blended in a chitosan matrix, and
wet-spun to yield fibres of HC composites at 5, 15, 20 and 40% concentrations (mass fraction
of nHA). Scanning electron microscopy and energy-dispersive x-ray spectroscopy revealed a
uniform distribution of nanocrystallites within the fibre. Tensile testing revealed that HC
fibres, which comprised nHA treated at T = 100
◦
C, possessed low tensile strength, σ
0
, and
stiffness, E, at low nHA concentrations but high σ
0
and E at higher concentrations, i.e. beyond
a 15% mass fraction of nHA. However, with nHA treated at T = 40
◦
C, the fibres yielded high
σ
0
and E at low nHA concentrations but low σ
0
and E at high concentrations. The results
strongly implicate the underlying effect of crystallite morphology on stress transfer at different
concentrations.
1. Introduction
Hydroxyapatite (Ca
10
(PO
4
)
6
(OH)
2
) possesses the appropriate
osteoconductivity and biocompatibility for use in hard-tissue
replacement implants but as a monolithic material, it suffers
from brittleness [1]. This limits its role as a load-bearing
material. Fortunately, this brittleness can be overcome by
reducing the crystalline material to nanocrystallites [2]; these
crystallites can be incorporated into a biogradable polymer
matrix such as chitosan, a copolymer of N-acetyl glucosamine
and D-glucosamine extracted from crustacean shell wastes
[3–5], to yield hydroxyapatite-chitosan (HC) composites from
which the desired mechanical property can be tailored. Studies
on the HC composite for bone marrow implants revealed no
inflammation but more importantly, these reports showed that
a new bone could form around the implant [1]. Results
from experiments have shown that small concentrations of
nHA favour high tensile strength (σ
0
) and stiffness (E) of HC
composites [6] in contrast to predictions from finite element
models [7]. Underlying the influence on the mechanical
properties of HC composites is the morphology of nHA
crystallites; this was not addressed in [6]. Interestingly,
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