Plasma sprayed coatings of hydroxylapatite

K. de Groot
Department of Biomaterials, Free University. P. 0. Box 7161, Amsterdam, The Netherlands

R. Geesink
Department of Orthopedics, State University, S t . Annadal 1, Maastricht, The Netherlands

C. P. A. T. Klein
Department of Biomaterials, Free University, P. 0. Box 7161, Amstwdam, The Netherlands

P. Serekian
Osteonics Inc., Allendale, New Jersey

The technique of plasma spraying has been
applied to deposite a thin, dense layer of
hydroxylapatite onto a titanium substrate.
Bond strength of such apatite coatings with
the substrate have been measured, as well
as the (absence of) influence of the coating
process on fatigue properties of the sub-
strate. Animal studies showed similar his-
tological reactions to apatite coatings as to
(well documented) apatite bulk materials.

INTRODUCTION

It has been well documented that living bone may show a strong bond
with implants made of sintered hydroxylapatite,'r2hereafter called HA. Due
to this phenomenon, implants with a surface of HA are called bioactive. On
the other hand, implants having only intimate contact with bone are called
bioinert. Therefore, both bioactive and bioinert implants can be os-
seointegrated (= having close contact with bone) after implantation, but only
bioactive implants show bonding with bone as
Unfortunately, the biomechanical properties of sintered HA are poor.
Although a compressive strength of up to 600-700 MPa may be achieved and
a tensile strength of up to 200-250 MPa, the resistance against fatigue failure
is very low. Normal physiological tensile loading causes fatigue fracture of
dense HA tooth implants within several months. The conclusion therefore is
that HA implants can only be applied if either no forces at all, or only
compressive forces, act on the implant.'
Therefore, it has been suggested to use thin coatings of HA on metalIic
substrates if tensile loading is to be expected (p. 216, ref. 1). The thickness
of such a coating must be a compromise between two limiting conditions. On
the one hand, the thinner a ceramic coating, the better its mechanical prop-
erties, and on the other hand, our finding that within the first few months
15-20 Frn of a HA surface may dissolve as stated in Ref. 4. In this reference,

Journal of Biomedical Materials Research, Vol. 21, 1375-1381 (1987)

0 1987 John Wiley & Sons, Inc. CCC 0021-9304/87/'121375-07$04.00
1376 DE GROOT ET AL.

experimental data from an earlier publication (ref. 17 in this reference) were

recalculated in terms of the increase of average pore diameter, the increase
assumed to be caused by resorption. The required compromise leads to a
thickness of about 50 pm.
In this publication we will describe mechanical and biological properties of
a 50-pm-thick HA coating on titanium substrates, obtained by means of
plasma spraying.

MATERIALS AND METHODS

Plasma spraying

Figure 1. shows schematically the principle of plasma spraying5 A DC

electric arc is struck between two electrodes, while a stream of (mixed) gases
passes through this arc. This results in an ionized gas of high temperature
up to 30000°C, with a high-speed approaching the speed of sound due to the
large expansion resulting from this temperature increase.
Hydroxylapatite powder is suspended in a carrier gas stream which is fed
into the plasma flame.
The thickness of the coating varied between 40 and 54 pm, as measured
by micrometer, and surface profilometry.

plasma s p r a y i n q

powder

11
anode /: * ...

plasma

Figure 1. Schematic overview of a plasma spray machine.

PLASMA SPRAYED COATINGS OF HYDROXYLAPATITE 1377

Substrate

Literature data6r7show that hydroxylapatite reacts with titanium and its

oxides at elevated temperatures, creating a chemical bond between coating
and substrate. Since conditions such as encountered by plasma spraying may
initiate such reactions as well, we choose titanium, either pure or in alloy, as
substrate.

Powder

The powder used for coating was either produced in our laboratory, or
obtained commercially from Merck.

Mechanical testing

Fatigue testing of the coating was performed according to Moore.8 The

shear strength of the bond between metal and coating was measured, as well
as the shear strength of living bone to coated and uncoated titanium plugs
(see Refs. 2,5).

Animal testing

Cylindrical rods of Ti-6A1-4V titanium alloy were prepared, measuring

4.5 x 6 mm. A hydroxylapatite coating of 50 pm thickness was applied using
the plasma spray technique, described above. Using sterile surgical tech-
niques, the plugs were inserted into predrilled holes in the lateral cortex of
adult canine (labrador) femora. To avoid mechanical retention, the holes
were slightly oversized (4.7 mm). During drilling of the holes cooling was
applied. A total of 42 hydroxylapatite coated plugs were inserted into the
femora of 7 dogs (3 plugs per femur). There were no surgical complications.
The dogs were left on full weight-bearing from the beginning. After follow-
up periods of 6 weeks and 3, 6, and 12 months the dogs were sacrificed.
After radiography the femora were used for histological examination and
mechanical testing.
After removal of excess soft tissue the femur was sectioned in three pieces
each one with one plug.
Two of these plugs were used for mechanical testing. The femoral pieces
containing these plugs were sectioned longitudinally, to gain access to the
intramedullary part of the plug. The bone pieces were positioned in a testing
jig to allow accurate lining of the loading axis with the long axis of the plug.
The plugs were pushed out from the surrounding bone using a Zwick test
machine with a crosshead speed of 1mm/min. The maximum force to loosen
the implant was calculated from the load-displacement curves. To calculate
the shear strength of the interface, the extraction force was divided by the
1378 DE GROOT ET AL.

total bone contact area. The bone contact area was calculated using the
formula A = 3,14.d.h., where d is the diameter of the implant with the
coating (4.6 mm) and h is the cortical thickness around the implant.
One implant from each femur was selected at random and left intact for
histological examination. After formalin fixation and alcohol dehydration the
implants were embedded in polymethylmethacrylate. Next, 100 pm thick-
ness sections were prepared using a lowspeed diamond cutting wheel with
cooling. These sections were used for microradiographic observations.
For light microscopy sections of 7pm were prepared by using a Jung K
microtome, after removing the implant material by a milling machine and
reembedding the cavity with polymethylmethacrylate.

RESULTS

Mechanical testing of coating to Ti

Table I displays the results of fatigue studies, as well as those of shear

stress required to remove the coating.
Push-out testing of coated and noncoated plugs showed that noncoated
plugs had no measurable adhesion to bone while apatite coated surfaces
required a stress of 55 MPa (after 3 months) and 62 MPa (after 6 months) to
be removed from the implant bed (see Table 11).

TABLE I
Strength Properties of Titanium Coated with Hydroxylapatite (HA)
~ ~~

Fatigue Tensile Strength at 10' Cycles

HA-coated Ti F-136 alloy 54 MPa
Noncoated alloy 57 MPa
HA-coated Ti F-67 alloy 25 MPa
Noncoated alloy 26 MPa

Tensile bond strength of coating to substrate

HA coating on Ti F-136 83 MPa

TABLE I1
Push-Out Test of Ti Plugs, Coated and Uncoated
with HA Shear Strength in MPa (standard error: zk207c)
Time postoperative
Ti plugs with HA Ti plugs without HA (inviith)

50 0,6 1,5
55 0.6 4
62 6
PLASMA SPRAYED COATINGS OF HYDROXYLAPATITE 1379

Animal testing

From the microradiographs we deduced that within 6 weeks of implanta-

tion defects of periosteum and slits space in the cortex around the implants
were completely filled with bone (see Fig. 2).
Periosteal and endosteal bone were proliferated along the surface of the
implant,which protruded respectively out and in the femur bone. In the
medulla the endosteal bone was seen to proliferate all along the surface of
the implant and bone trabeculae had grown into the marrow cavity.
From the light microscopy we have seen a close contact of the newly
formed bone with the implant. The new bone showed remodeling, the
lacunae bordered both implant and lost bone. In the lacunae many active
osteoblasts, osteoclasts and osteoid could be observed. Small zones of oste-
oid were situated along the implant. The new bone was of a lamellar and
woven structure (Fig. 3).

Figure 2. Microradiograph after 6 weeks of implantation in a dog femur. (a)

proximal section, (b) distal section see also schematic drawing. The arrows
points to new bone formation against the implantmaterial.
1380 DE GROOT ET AL.

Figure 3. Lightmicroscopy photograph after 6 weeks of implantation in a

dog femur. The bone is grown against the implantmaterial (Imp). The bone
shows remodelling lacunae (L), which contain osteoblasts and some osteo-
clasts.

In the endosteal part, many granulocytes and plasmacells were seen after
6 weeks of implantation. After 12 weeks of implantation the amount of
inflammatory cells was decreased.

DISCUSSION

It is obvious from the in v i m measurements that the major disadvantage

of bulk apatite ceramics, namely, their susceptibility for fatigue failure, does
not occur with 50-pm-thin coatings of apatite on titanium substrates: there
is no measurable difference in the fatigue strength of HA coated titanium and
uncoated titanium. This shows, in addition, that the titanium surface is not
altered with respect to fatigue behavior by being coated with HA.
Push-out tests made clear that bone bonding to HA coatings is essentially
the same as to HA bulk implants: this is not very surprising but shows
nevertheless that from a bonding point of view no measurable difference
exists between a plasma sprayed apatite surface and a sintered apatite
surface.
Table I11 shows this clearly.
The difference in bonding between uncoated and HA coated titanium
plugs is striking. In agreement with some of the literature’ no bonding exists
with titanium. The only way to achieve retention of titanium implants is
PLASMA SPRAYED COATINGS OF HYDROXYLAPATITE 1381

mechanical: by means of undercuts."." On the contrary, bonding between

coated plugs and surrounding bone approaches the shear strength of bone,
a phenomenon reported many times for HA implants made by sintering.
This shows again that there exists an essential difference between the inert
material titanium by means of which only a close contact with bone can be
achieved (= osseointegration), and the bioactive apatite, which not only
shows osseointegration but bone bonding as well.
The reason for the appearance of lymphocytes and plasmacells is not clear.
We have seen these cells with several implantmaterials in different animal
species, mostly in soft tissue. Maybe they are due to mechanical irritation
due to initial micromovements of the -sometimes -ill-fitting implants.
These results are in our opinion encouraging for the development of HA
coated implants.

References
1. K. de Groot, "Degradable ceramics," in Biocompatibility of Clinical lmplaizf
Materials, Val. I , D. F. Williams (Ed.), CRC Press, Boca Raton, 1981,
199-222.
2. M. Jarcho, "Calciumphosphate ceramics as hard tissue prosthetics,"
Clin. Orfhop. Rel. Res., 157, 259-278 (1981).
3. I? I. Branemark, et al., Osseointegrated Implants, Almqvist and Wiksell
International, Stockholm, 1977.
4. C.A. van Blitterswijk, J. J. Grote, W. Kuypers, W.Th. Daems, K.
de Groot, "Macroport tissue ingrowth: a quantitative and qualitative
study on hydroxyapatite ceramic," Biomaterials, 7, 137-144, (1986).
5. R. F. Bunshah (Ed.), Deposition Technologiesfor Films and Coatings, Noyes
Publications, Park Ridge, NJ.
6. J. L. Lacout, J. Assarane, J. C. Trombe, "Sur la fixation du titane par les
minerais phosphates," C. R.Acnd. Sc.Paris, 298, Serie 11, 173-175 (1984).
7. P. Ducheyne, W. van Raemdonck, J . C. Heughebaert, and M.
Heughebaert, "Structural analysis of hydroxylapatite coatings on titan-
ium," Biomaterials, 7, 97-104 (1986).
8. H. F. Moore, "Fatigue tests," in Metals Handbook, Publ.American Society
for Metals, 1948, pp. 118-124.
9. E. Barth, H. Ronningen, and L. F. Solheim, "Comparison of ceramic and
titanium implants in cats," Acfn Orthop. Scand., 56, 491-495 (1985).
10. J. D. Bobijn, P. M. Pilliar, H. U. Cameron, and G. C. Weatherly, "The
optimum pore size for the fixation of porous surfaced metal implants by
the ingrowth of bone," Clin. Orthop. Rel. Res., 150, 263-270 (1980).

Received September 18, 1986

Accepted July 21, 1987