Surface Structure of the Total Joint Replacement after Hydroxyapatite Application

F. Onderka a, D. Dobrocký b
a
24th Air Transportation Base, Mladoboleslavská 300, 197 00 Praha 9 – Kbely,
Czech Republic
b
Department of Mechanical Engineering, University of Defence in Brno, Kounicova 65,
602 00 Brno, Czech Republic

Given that CoCr alloys have excellent corrosion resistance and

abrasion resistance, they have found their wide use as a material
for replacing human joints, especially the knee and hip
replacements (1, 2). CoCr alloys offer a wide range of positive
mechanical properties such as high strength, hardness and
elasticity. However, despite all the advantages in these alloys are
occurring the following problems: corrosive processes that
increase the level of metal ions in the local tissues, and systems (in
blood) (3), adverse micro and nanotopography of surface, low
biological activity, non-hydrophilic surface (2). New approaches
are currently looking to reduce the amount of wear particles whilst
maintaining the required biocompatibility of the material. The
work is focused on the evaluation of surface structure CoCrMo
alloy, which is used to produce joint replacements, after the
deposition of hydroxyapatite by electrochemical method. The
carbon nanotubes (CNT) were added to improve the mechanical
properties of the deposited coating of hydroxyapatite.

Introduction

Hydroxyapatite (HA) is a bioceramic material with poor mechanical properties,

especially for bearing applications (4). It has low toughness and poor bending strength
(MPa ˂ 140) (5). However, the hydroxyapatite has a structure similar as bone, and can
support the growth of living tissues, because it contains virtually equal proportions of
calcium and phosphorus, as human bone (6, 7). With this feature, it is a synthetic HA
used in bone augmentation. In combination with CoCrMo alloy creates the biomaterial
having excellent mechanical and biological properties (6). The primary role of HA is a
biological activity, secondary role is increasing the resistance of the metal in the
physiological environment, minimization or prevention of release ion into the
surrounding tissue and reducing the risk of corrosion (7). The main advantages of the
synthetic HA are its biocompatibility, slow biodegradation in situ and good
osteoconductive and osteoinductive possibility (4). In 1991, Sumio Iijama discovered
CNT having an outer diameter of 4 to 30 nm and lengths up to 1 mm (5, 8). CNT excel
specific structural characteristics, such as very small size, low density, high tensile
strength (~60 GPa), high Young's modulus (up to 1 TPa) and excellent toughness,
excellent flexibility, excellent thermal and electric properties (5, 9). Due to the above-
mentioned properties and effects appear CNT as a potential reinforcement for the HA in
order to improve its mechanical properties. Research the combination of HA-CNT was
launched recently (2004), therefore, also due to the ambiguity in biocompatibility, the
combination of HA-CNT in commercial production joint replacements is not used (9).

Experimental material and methods

For the preparation of the specimens were chosen cast CoCrMo alloy rollers of
labeled B and M. Analysis of the chemical composition of the surface of the substrate of
alloy CoCrMo (ISO 5832-4) was performed on a Noran EDS System SIX/300 and it is
listed in Table I.

TABLE I. Chemical composition of CoCrMo alloy

Chemical composition wt (%)
Element Cr Mo Fe Si P Ti Co
Specimen B 31.46 5.81 - 2.5 - - 60.23
Specimen M 30.22 4.81 - 1.47 - - 63.50

The solution used for the preparation of hydroxyapatite by electrochemical method

contained 800 ml of distilled water, 7.936 g of Ca(NO3)2 4H2O and 2.304 g NH4H2PO4
(10). Elimination was held at a bath temperature of 65 °C. An aluminum sheet was used
as an anode, it was cleaned in Nital (5%), then was ultrasonically cleaned in ethanol and
air dried. Samples labeled as B and M were using conductive carbon glue attach upon a
thin copper strip. Sample surface was grinded before depositing hydroxyapatite through
the use of sandpaper firm HERMES with grit abrasives 1000, due to increase the
adhesion of the electrochemically excreted HA coating (11). Deposition parameters of the
coating are listed in Table II. At first, the coating was applied to sample B then the CNT
from Sigma-Aldrich® Company were added to the solution, the parameters of CNT are
provided in Table III. The amount of the CNT in the solution was 5% by volume. Sample
M was mounted at an angle of approximately 45 ° and the solution was throughout the
process regularly mixed due to better deposition of the CNT on sample during deposition.
The actual amount of the CNT in coating then depends on the inclination of the sample
during the deposition (in the horizontal position the quantity will the largest, the smallest
in vertical position) and the intensity of mixing of the solution.

TABLE II. Deposition parameters of hydroxyapatite coating for samples B and M

Element Time [h] Current density [mA·cm-2]
Specimen B 1 2
Specimen M 1 2.4

Acquisition visual documentation was using an optical microscope Olympus SZX9

with QuickPHOTO Industrial Software v2.3. Further images were taken using a scanning
electron microscope Quanta 450 FEG. EDS analysis was performed at three points on
each sample, these points are marked in red on the picture 5 and 15, at these points
chemical composition was also measured (Table 4 and 5). From the measured values
were calculated Ca/P ratio which were rounded to two decimal places. Within
observation were also by the help of electron microscope Quanta 450 FEG, CNT
acquired images (see Figure 11 to 14) and by use the software was measured length and
diameter, which are plotted red in Figure 11-13.
TABLE III. Parameters of CNT
Parameter Unit Value
Type [-] MWCNT
Structure [-] Carbon, > 90 %
diameter [µm] 5-9
Dimensions
length [µm] 110 - 170
Melting point [°C] 3652 - 3697
-1
Density at 25 ° C [g·ml ] 1.7

Results and discussion

Deposited coatings of HA on both samples were white to gray-white colour and in

observation of the eye coherently covered the entire surface of the sample. When
observing by optical microscopes at lower magnifications (Figure 1 and 2) can already be
seen discontinuities in coating in the form of pores or spots on the surface where the
coating not adhering or not created. The coating of sample B is coarser with relatively
evenly distributed larger crystals (Figure 3). With greater current density of deposition of
the coating and adding CNT on sample M was created finer structure which is formed
finer acicular particles, coarser crystals there occurred rather infrequently (see Figure 4).
Both coatings are very space-distinctive, crystals grow during deposition in the direction
from the substrate surface and 3D macro porous structure is created.

Figure 1. Structure of HA coating, the sample B, Figure 2. Structure HA+CNT coating, sample M,
an optical microscope an optical microscope

Figure 3. Structure of HA coating, the sample B, Figure 4. Structure HA+CNT coating, sample M,
an optical microscope an optical microscope
 Pictures taken with an electron microscope further approach the structure of the
coating. The structure of the coating B is very diverse (Figure 5). A closer observation of
areas of the sample B, which are at the interface between the coarse and finer crystals, we
can to determine that they consist of smaller and finer crystals (Figure 6). These crystals
have a very fine porous structure which is at the level of nanometres (Figure 7). The EDS
analysis was carried out in point 1, which corresponds to rougher crystal; point 2
corresponds to a very fine structure. Point 3 is the observed entire area of sample B. The
measured points are red marked on Figure 5.

Figure 5. Structure of HA coating with measured points (red marked), sample B, an electron microscope

Figure 6. Smaller and finer crystals in structure of Figure 7. Porous structure of HA coating, sample B,
HA coating, sample B, an electron microscope an electron microscope

All three measurement points are rich in oxygen, phosphorus, and calcium. The exact
chemical composition in atomic percent is shown in Table 4. Ca/P ratio indicates the kind
of apatite.

TABLE IV. The chemical composition of the sample B in points 1, 2 and 3

Sample B O at [%] P at [%] Ca at [%] Ca/P [-]
Point 1 77.09 11.69 11.22 0.96
Point 2 65.98 15.07 18.96 1.26
Point 3 68.72 14.00 17.28 1.23
 Areas of B sample with finer structure exhibit very fine and complex hairy structure
(Figure 8). In some areas the hairy structure was formed, where the fibres diameter are in
the order of nanometers and a length of tens to hundreds of nanometres (Figure 9). The
situation is similar in the other point of the sample where was observed also hairy until
the dendritic structure, the length of the fibres is however shorter and they have a larger
diameter (Figure 10).
Carbon nanotubes have been observed separately, prior to addition to the solution for
preparing of hydroxyapatite. In order to verify the dimensions mentioned by
manufacturer, measurements of diameter nanotubes were carried out, which is shown in
Figure 11 and 12. Verification of the length is then in Figure 13. Figure 14 shows an
overall view of the nanotubes.

Figure 8. Area with finer structure of HA coating, Figure 9. Hairy structure of HA coating, sample B,
sample B, an electron microscope an electron microscope

Figure 10. Hairy until dendritic structure of HA Figure 11. CNT, diameter measurement, an electron
coating, sample B, an electron microscope microscope
Figure 12. CNT, diameter measurement, an electron Figure 13. CNT, length measurement, an electron
microscope microscope

Figure 14. Overall view of the CNT, an electron microscope

The EDS analysis was, in the case of sample M, again performed at three points (see
Figure 15). In the first section designated as point 1 which corresponds to rough crystal;
in the second point (point 2) which corresponds to a very fine structure. Point 3 is the
whole observed area of sample M. All three measured points are as well as in the case of
the sample B rich on oxygen, phosphorus and calcium. Slight amount of aluminium
which during deposition released into solution from the anode was appeared in point 2.
The exact chemical composition in atomic percent is shown in Table 5. Ca/P ratio
indicates the kind of apatite.

TABLE V. The chemical composition of the sample M in points 1, 2 and 3

Sample B O at [%] P at [%] Ca at [%] Al at [%] Ca/P [-]
Point 1 74.63 12.80 12.57 - 0.98
Point 2 68.13 14.50 17.03 0.34 1.17
Point 3 72.27 13.11 14.62 - 1.12

As with the previous sample is a structure of the coating of sample M heterogeneous

(Figure 15). The figure shows that the coarser crystals covered a larger area than a finer
portion of the coating. At a closer observation of coarse crystals of coating we can
observe its construction in layers (Figure 16). The finer part is different from finer parts
of sample B. The construction is also hairy, but the fibres are finer and thicker, the length
and the diameter is in units of nanometres, the structure resembles a foam structure
(Figure 17 and 18).

Figure 15. Structure of HA+CNT coating with Figure 16. Coarse crystals in structure of HA+CNT
measured points (red marked), sample M, coating, sample M, an electron microscope
an electron microscope

Figure 17. Foam structure of HA+CNT coating, Figure 18. Foam structure of HA+CNT coating at
sample M, an electron microscope higher magnifications, sample M, an electron
microscope

On the deposition and the resulting morphology of the hydroxyapatite have an

influence of quantities deposition, i.e. deposition length and current density. During the
deposition of coatings on both samples was used the same time (1 h), but the current
density was different. With increasing current density the morphology of the coating was
changed. A finer structure originated, length of the fibres is shortened, and probably is
reduced their diameter. The coarser crystals have not practical use as a coating for
improving the osteointegrating properties of implants. Conversely, a suitable structure
utilizable in practice exhibit finer porous areas, such as the Figure 10 and 18. The key
role plays not only voltage, but also the electrolyte concentration (10).
 Conclusion

On the resulting structure of hydroxyapatite which was deposited by electrochemical

method had an effect a selected current density. The most suitable structure which was
achieved can be considered a porous structure in some places the sample M (see Figure
18). A persistent problem with a hydroxyapatite excluded electrochemically remains its
bad adhesion to the base material, which must be at least 15 MPa (12). Adhesion for
different methods for preparing of hydroxyapatite coating compares literature (13).
Generally, it can be stated that the increase in the current density led to the formation of
finer areas in the coating however it also increased the area which is occupied by coarser
crystals. Attention must also be paid to the choice of the anode material. Application of
special biocompatible coating - hydroxyapatite coating on the alloy CoCrMo - could find
use in case of cementless joint replacements, however, it is necessary to solve the
problem with a lack of adhesion and devote to attention of problem of biocompatibility of
the CNT.

Acknowledgments

The work presented in this paper has been supported by the specific research project
2015 at the Department of Mechanical Engineering, University of Defence in Brno.

References

1. M. Mori, K. Yamanaka, H. Matsumuto, A. Chiba, Evolution of cold-rolled

microstructures of biomedical Co-Cr-Mo alloys with and without N doping, in
Materials Science and Engineering, 2010, 528, p. 614–621.
2. J. A. García, C. Díaz, S. Mändl, J. Lutz, R. Martínez, R. J. Rodríguez,
Tribological improvements of plasma immersion implanted CoCr alloys, in
Surface & Coatings Technology, 2010, 204, p. 2928–2932.
3. R. Sonntag, J. Reinders, J. P. Kretzer, Alternative materials for articulation in
total joint replacement, in Acta Biomaterialia, 2012, 8, p. 2434–2441.
4. H. Zhou, J. Lee, Nanoscale hydroxyapatite particles for bone tissue engineering,
in Acta Biomaterialia, 2011, 7, p. 2769–2781.
5. S. Mukherjee, B. Kundu, S. Sen, A. Chanda, Improved properties of hydrox-
yapatite-carbon nanotube biocomposite: Mechanical, in vitro bioactivity and
biological studies, in Ceramics International, 2014, 40, p. 5635–5643.
6. A. Arifin, A. B. Sulong, N. Muhamad, J. Syarif, M. I. Ramli, Material processing
of hydroxyapatite and titanium alloy (HA/Ti) composite as implant materials
using powder metallurgy: A review, in Materials and Design, 2014, 55, p. 165–
175.
7. J. Faig-Martía, F. J. Gil-Murb, Hydroxyapatite coatings in prosthetic joints, in
Rev. esp. cir. Ortip. Traumatol., 2008, 52, p. 113–120.
8. S. Iijima, Carbon nanotubes: past, present, and future, in Physica B, 2002, 323, p.
1–5.
9. D. Lahiri, S. Ghost, A. Agarwal, Carbon nanotube reinforced hydroxyapatite
composite for orthopedic application: A review, in Materials Science and
Engineering, 2012, 32, p. 1727–1758.
10. Y. Zhang, J. Tao, Y. Pang, W. Wang, T. Wang, Electrochemical deposition of
hydroxyapatite coatings on titanium, in Transactions of Nonferrous Metals
Society of China, 2006, 16, p. 633–637.
11. N. Eliaz, O. Ritman-Hertz, D. Aronov, E. Weinberg, Y. Shenhar, G. Rosenman,
M. Weinreb, E. Ron, The effect of surface treatments on the adhesion of
electrochemically deposited hydroxyapatite coating to titanium and on its
interaction with cells and bacteria, in Journal of Materials Science Materials in
Medicin, 2011, 22, p. 1741–1752.
12. Implants for surgery – Hydroxyapatite – Part 2: Coatings of hydroxyapatite. 2008.
ISO 13779-2.
13. E. Mohseni, E. Zalnezhad, A. R. Bushroa, Comparative investigation on the
adhesion of hydroxyapatite coating on Ti–6Al–4V implant: A review paper, in
International Journal of Adhesion and Adhesives, 2014, 48, p. 238–257.