Review Article

Nano‑hydroxyapatite and its contemporary applications

Nidhi Kantharia, Sonali Naik1, Sanjay Apte1, Mohit Kheur, Supriya Kheur2, Bharat Kale1

Department of Prosthodontics,
M. A. Rangoonwala Dental College,
Abstract
1
Center for Materials for Electronics
Combination of nano‑sized hydroxyapatite (nHA) with restorative materials like glass ionomer cement and
Te c h n o l o g y, 2 D e p a r t m e n t o f
Oral Pathology, DPU’s D. Y. Patil composite resins has been reported recently in 2011. The documented effects of these nano‑sized particles on
D e n tal College ,   Pimpr i, P une, the chemistry of these materials include increased biocompatibility and mechanical strength. nHA has been
Maharashtra, India utilized for various applications like pulp capping agent, root canal sealer, filler for bleaching agents and
toothpastes, osseo‑conductive bone graft etc., A nHA has been obtained using natural bovine bone, carbon
Access this article online template technique, hydroxyapatite‑chitosan template technique, wet precipitation technique, plasma
spraying technique etc. This paper presents a review of the various aspects of nHA and summarizes the
Website: www.iadrsd.org
methods of fabrications and potential clinical applications of the same.
Quick response code

Key words: Clinical applications, nano‑sized hydroxyapatite, techniques

Introduction crystallography and chemical composition to that of human

Developments in material science, robotics, and biomechanics
have dramatically changed the technique of replacing any
component of human anatomy with restorative material.
Restorative dental materials are subjected to a very hostile
environment, in which pH, salivary flow and mechanical
loading fluctuate rapidly and constantly. The toxicity of tissues
due to materials is gaining more attention with the availability
of variety of materials, thus drawing attention of federal
agencies.[1] With the development of nanotechnology, a major
impact on materials science has been noted. In this century,
the production of materials with nanostructures has gained
much attention for adsorption, catalytic, biomaterials and
optical applications.[2]
Hydroxyapatite is the main biomineral component found in
human hard tissues, i.e. tooth and bone. Its stoichiometry is
represented by the formula (Ca10 (PO4) 6 (OH)). It is comprised of
calcium and phosphorus present in the ratio (Ca/P) of 1.67.[3] It
is the main mineral component of the enamel, comprising of
more than 60% of tooth dentine by weight [Table 1].[4,5]
Hydroxyapatite has attracted much interest as a biomaterial
for use in prosthetic applications due to its similarity in
hard tissue.[2] On account of its outstanding properties like
biocompatibility, bioactivity, osteoconductivity, non‑toxicity
and non‑inflammatory nature,[6] this bioceramic has got a
variety of applications which include: Bone tissue engineering;
restoration of periodontal defects; [7,8] edentulous ridge
augmentation;[9] orthopedic and dental implant coating,[10‑12]
endodontic treatment like pulp‑capping, repair of mechanical
bifurcation perforations and apical barrier formation,[13‑15] fillers
for reinforcing restorative glass ionomer cement (GIC)[4,16‑22] and
restorative composite resin; [23‑37] desensitizing agent post
bleaching;[38] for treating early carious lesions[39‑41] and as a
remineralizing agent in toothpastes.[42]
In an article in 1975, Nery et al., for the first time in dentistry,
studied the effect of tricalcium phosphate reagent in intrabony
defects in dogs, but later it was demonstrated that the
phosphate was a mixture of hydroxyapatite and tricalcium
phosphate.[43,44]
Hydroxyapatite is manufactured in many forms and can be
prepared as a dense ceramic,[45] powder,[46] ceramic coating[47]
or porous ceramic[48] as required for the particular applications.
However, in recent years, nano‑sized hydroxyapatite (nHA)
with appropriate stoichiometry, morphology and purity have

Correspondence to: Dr. Nidhi Kantharia, 1132/3, Vishnu Darshan, F. C. Road, Shivajinagar, Pune ‑ 411 016, Maharashtra, India.
E‑mail: nidhikantharia12@gmail.com

Journal of Dental Research and Scientific Development | 2014 | Vol 1 | Issue 1 15

 Kantharia, et al.: Restorative applications of nano-hydroxyapatite

stimulated great interest in scientific research. It is believed
that nHA with grain size <100 nm in at least one direction has
a high surface activity and ultrafine structure similar to the
mineral found in hard tissues [Figure 1].[49]
With the advent in technology and developing interest, diverse
methods for fabricating hydroxyapatite have been reported in
the literature. According to a review published by Sadat‑Shojai
et  al., various methods for preparing hydroxyapatite can
be widely classified into-dry methods, wet methods, high
temperature processes, synthesis from biogenic sources and
combination of above stated procedures [Table 2].[49]
Among all the methods, chemical precipitation, combination
methods and hydrothermal processes are the most popular
methods for fabricating nHA.
The mechanical properties of hydroxyapatite are greatly
determined by the morphology and crystallography of the
particles, which in turn demands on the mode of fabricating
Hydroxyapatite.
Materials and Methods
The electronic database chosen for developing this review was
PubMed database. Following keywords were used for searching
relevant papers: (nanohydroxyapatite or hydroxyapatite)
and (dental restorations or restorative material or composite
resins or GIC or pulp capping agents or root canal filling
agents). Papers were selected if the combination of words
appeared anywhere in the paper, were published over the time
period of 25 years (1987‑2012) and were written in English.
The reference list of each paper was reviewed and any paper
appearing in the reference list was added to the list of papers
to be manually reviewed. A total of 127 papers were retrieved
from the PubMed database, out of which only 39 papers
Table 1: Chemical comparison of teeth, bone and
hydroxyapatite
Constituent Ca P Ca/P ratio
Enamel 36.5 17.1
Dentin 35.1 16.9
Bone 34.8 15.2
Hydroxyapatite 39.6 18.5
Ca=Calcium, P=Phosphorous
were chosen which presented the use of hydroxyapatite
particularly in restorative dentistry. The remaining papers
listed in the reference list of this paper are regarding the
various techniques of manufacturing hydroxyapatite and the
conventional restorative materials used in dentistry.
The main aim of this paper is to review the literature for various
studies done on hydroxyapatite as a restorative material for
various clinical use.
Results of Restorative Applications of nHA
Fillers in restorative GICs
The first glass ionomer material was introduced by Wilson
and Kent in 1972 as a “new translucent dental filling material”
recommended for the restoration of cervical lesions.[50,51] The
glass ionomer family of restorative materials has evolved over
the past 40 years into a diverse group of products including
liners, bases, restorative materials, luting agents as well as
pit and fissure sealants; all available in both the conventional
and resin modified varieties.[51] The vast indication of GIC
is attributed to their beneficial properties, which include
fluoride release and recharge ability, marginal sealing, chemical
bonding to dental structure, biocompatibility and co‑efficient
of thermal expansion similar to that of the tooth structure.
Despite these outstanding advantages, there are well‑known
shortcomings associated with GIC, such as the sensitivity to
moisture contamination and desiccation and poor mechanical
properties.[22]
The effect of adding hydroxyapatite to GIC was first studied by
Nicholson et al.[16] in 1993 and since then has directed research
in this field.
A study by Yap et al.[17] stated that addition of hydroxyapatite
particles of the size range from 0.3 to 50 microns 12% by volume
to restorative GIC would result in improvement of mechanical
properties.
1.63
1.61
1.71
1.67

Table 2: Methods of preparing hydroxyapatite

Methods Subtypes
Dry methods Solid state, mechanochemical
Wet methods Chemical precipitation, hydrolysis, sol‑gel
High temperature Combustion, pyrolysis
processes
Synthesis from Example‑bone waste, eggshell,
biogenic sources exoskeleton of marine animals etc.,
Combination Example‑hydrothermal+mechanochemical,
Figure 1: Field emission-scanning electron microscopy image of nanosized
procedures hydrothermal+hydrolysis hydroxyapatite

Journal of Dental Research and Scientific Development | 2014 | Vol 1 | Issue 1 16

 Kantharia, et al.: Restorative applications of nano-hydroxyapatite
Arita et  al.[18,19] in their study have reported that adding
nHA (Whiskers and Granules) improved the flexural strength
and microstructural properties of GIC. While whiskers
showed better strength, granules when added 8% by mass
also improved the flexural strength. The same author carried
out another study in 2011[22] in which hydroxyapatite particles
of varying sizes were added to GIC 8% by mass to enhance
the mechanical and chemical properties of the cement. They
concluded that conventional restorative GIC can be improved
by incorporating highly reactive hydroxyapatite particles of
10 microns diameter.
Gu et al.[20] carried out the addition of zirconia powder with
nHA in restorative GIC and achieved improved mechanical
properties over hydroxyapatite when used alone. Such
difference in the results was attributed to high strength, high
modulus, hardness and insoluble nature of zirconia.
In a study conducted by Lee et  al.[21] the bond strength and
resistance to demineralization was significantly enhanced by
adding 10% nanoscopic hydroxyapatite.
Goenka et al.[4] formulated bioactive nanocrystalline calcium
deficient hydroxyapatite  (nCDHA) GIC composite cement
by adding nCDHA (5, 10 and 15 wt %) to conventional
glass powder. They concluded that the addition resulted in
increased compressive strength and resorption potential of
the cement.
Fillers in restorative composite resin
Composite resins have been introduced into the field
of conservative dentistry to minimize the drawbacks of
the acrylic resins that replaced silicate cements (the only
aesthetic materials previously available) in the 1940s. In
1955, Buonocore[52] used orthophosphoric acid to improve
the adhesion of acrylic resins to the surface of the enamel. In
the year 1962 Bowen[53] developed the Bis‑phenol A‑glycidyl
methacrylate (Bis‑GMA) monomer in an attempt to improve
the physical properties of acrylic resins, as their monomers
only allowed linear chain polymers to be formed. Today most
composites used in dentistry are hybrid materials, so‑called
because they are composed of polymer groups reinforced by
an inorganic phase of glass fillers with different compositions,
particle sizes and fill percentages. Flowable or condensable
composites have attempted to provide an answer to certain
functional requirements, although they have not been too
successful at improving properties. Turning to polymerization
initiators, both conventional or high intensity halogen lamps
and light‑emitting diode curing lights which provide a gradual
increase in light intensity are very useful for reducing shrinkage
of the composite material.[52] The clinical choice of a composite
must consider whether priority should be given to mechanical
or esthetic requirements: If mechanical considerations are
paramount the material with the greatest volume of filler will
Journal of Dental Research and Scientific Development | 2014 | Vol 1 | Issue 1
be chosen; if aesthetic considerations predominate, particle size
will be the most important factor. Additional components such
as opaquers and tints make it possible to improve the aesthetic
results.[52] Despite the significant improvement of resin‑based
composite, restorative composites still suffer from two key
shortcomings: Deficiencies of mechanical strength and high
polymerization shrinkage, which are responsible for the shorter
median survival lifespan of resin based composites (5‑7 years)
in comparison with amalgam (13 years).[29‑32,34]
Addition of hydroxyapatite as a filler particle to composite
resin was first reported in 1988 by Okazaki and Ohmae[23]
which resulted in improvement of mechanical properties
and biocompatibility only when the apatite to resin ratio was
maintained at 1.
Dupraz et  al.[24] investigated the effect of different coupling
agents on the hydroxyapatite powder incorporated into
composites as filler.
Santos et  al.[25] incorporated hydroxyapatite fillers (silane
treated and untreated) into the Bis‑GMa polymer. The effect
of silane treating hydroxyapatite particles resulted in better
contact with the polymer matrix. A similar study was carried
out by the same authors in 2002[26] for studying the water
absorption characteristics. They reported that lower water
uptake was seen when silane treated hydroxyapatite were
incorporated in composite, but the water solubility increased
with more incorporation of hydroxyapatite.
Arcís et al.[27] proposed that addition of hydroxyapatite should
be 50‑60 wt % to enhance the mechanical properties. The
author preferred microscopic hydroxyapatite over nHA as
filler particles.
Domingo et al.[28] also suggested that nanometric particles as
filler were unsuitable for clinical purpose. According to the
author, micrometric filler particles exhibited better hydrolytic
stability.
In contrast to the past, a recent report of Sadat‑Shojai et al.[33]
described a significant increase in bulk mechanical properties
and bond strength to dentine on adding hydroxyapatite
nanorods (0.2‑0.5 wt %).
According to a study performed by Chen et al.,[34] the critical
mass fraction of nHA fibers in resin should be around 10% to
influence the strength and mechanical properties.
Zhang and Darvell[37] demonstrated a positive variation in
mechanical properties with the addition of hydroxyapatite
whiskers. This variation was conferred due to properties like
good dispersibility and wettability of the whiskers with the
polymer. In the same year, Zhang and Wang[35,36] showed
accelerated photopolymerization of self‑etching adhesive
incorporated with hydroxyapatite.
17
 Kantharia, et al.: Restorative applications of nano-hydroxyapatite
Pulpotomy and direct pulp capping agent
The osseoconductive property of hydroxyapatite was exploited
for the purpose of pulp capping and pulpotomy back in 1992
by Jaber et  al.[54] In his animal study, hydroxyapatite was
compared with calcium hydroxide as a pulp capping agent
which showed a negative result as hydroxyapatite caused
dystrophic calcification in pulp, hence interfering with the
future endodontic treatment.
In a similar study by Sübay and Aşci,[55] hydroxyapatite as a
direct pulp capping agent did not induce hard tissue bridging
at the pulp exposure site.
Hayashi et  al.[56] conducted an animal study and concluded
that hydroxyapatite could directly substitute osteodentin when
used as direct pulp capping agent.
In an article in 2010, Shayegan et al.[57] have reported that nHA
did not cause any pulpal inflammatory response when used
as direct pulp capping agent while Shinkai et al.[58] reported
no significant changes on mixing hydroxyapatite in adhesive
systems for dentine bonding or direct pulp capping.
Kato et al.[59] in an animal study evaluated the histopathological
and immunohistochemical changes in pulp on adding different
forms of calcium phosphate to adhesive resin for the purpose
of direct pulp capping. The results showed that hydroxyapatite
and beta tricalcium phosphate had a tendency to produce a
larger amount of reparative dentine.
Fillers in endodontic root canal sealers
Hydroxyapatite was added to endodontic sealers by Gambarini
and Tagger[60] in 1996 as it was thought to influence the apical
healing and sealing ability. He concluded that it did not
adversely affect the sealing properties. In a recent report by
Collares et al.[61] adding nHA upto 40% to root canal sealers
did not alter its radio opacity and film thickness.
Treatment of early carious lesions
Li et al.[39] in 2008 referred as the “natural building blocks” of
enamel. According to them 20 nm sized hydroxyapatite particle
can effectively remineralize the enamel.
In the year 2011, Huang et  al. proved with the help of an
[40]
in vitro study that nHA can be used as an effective repair
material and anticaries agent with pH < 7. He also reported
that adding Galla chinesis along with nHA had a synergistic
effect on the remineralization of carious enamel.[41]
Conclusion
It may be stated that nHA is a versatile material with a multitude
of applications in various dental materials. Although proven
to have a significant impact on the properties of the material
it reinforces, more studies are required, especially to test and
quantify its efficacy under clinical conditions.
Journal of Dental Research and Scientific Development | 2014 | Vol 1 | Issue 1
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How to cite this article: Kantharia N, Naik S, Apte S, Kheur M, Kheur S,
Kale B. Nano‑hydroxyapatite and its contemporary applications. JDRSD
2014;1:15-9
Source of Support: Nil. Conflict of Interest: No conflict of interest.
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