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Microstructures of Plasma-Sprayed
Hydroxyapatite-Coated Ti-6Al-4V Dental Implants
Eser Tufekci, DDS, MS/William A. Brantley, PhD/John C. Mitchell, BS/Edwin A. McGlumphy,
DDS, MS
The purpose of this study was to investigate the microstructure of plasma-sprayed hydroxyapatite
coatings and the elemental composition near the coating-substrate interface for two commercial
implants, using the scanning electron microscope. Both coating surfaces and cross-sectioned
specimens were examined. The results indicated that while the surface microstructures of both
implants were consistent with the plasma-spraying process, the scale of the constituents was much
finer for one product. In cross-section, both coatings exhibited minimal porosity and intimate
contact with the titanium alloy substrate. It was found that limited interdiffusion of titanium and
calcium occurred near the interface.
(INT J ORAL MAXILLOFAC IMPLANTS 1997;12:25–31)
Key words: calcium phosphate, dental implant, hydroxyapatite, microstructure, osseointegration, plasma spraying,
scanning electron microscopy, titanium
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JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
plasma-sprayed coatings influence their dissolution. It is further thought that the continuous elemental
exchange occurring at the bone-implant interface makes the coatings highly unstable. Based on these
concerns, it has been predicted that the success rates of these coated implants would decrease over the
long term after placement.9,12 Nevertheless, more rapid and superior osseointegration between
HA-coated implants and bone, compared to noncoated titanium implants, has been reported.10
Although several publications6,11,13-16 have characterized the materials science aspects for
laboratory specimens of HA-coated titanium alloys (Ti-6Al-4V), there have been relatively few studies
that examined commercial implant products. The objective of the present study was to investigate those
microstructural characteristics of the coatings and elemental interdiffusion at the coating-substrate
interfaces that might affect the long-term clinical success of these implants.
Materials and Methods
Two commercial endosseous dental implants were selected for study: Integral (Calcitek, Carlsbad, CA)
and Bio-Vent (Dentsply Implant Division, Encino, CA). Both products are composed of plasma-sprayed
HA-coated Ti-6Al-4V. The implants were investigated with a scanning electron microscope (SEM)
(JSM-820, JEOL, Tokyo, Japan).
Study of the Coating Surfaces. For the surface study, two randomly selected implants from each
manufacturer were removed from the packaging and sputter coated with a thin gold-palladium film to
eliminate electrical charging during operation of the SEM. The cylindrical implants were examined, and
photomicrographs were taken at various magnifications to obtain information about the topography and
microstructural characteristics of the plasma-sprayed surfaces.
Study of Implant Cross-Sections and Elemental Analyses of Interfacial Regions. Three randomly
selected implants of each brand were used in this study. Before sectioning, to protect the thin HA
coatings,17 the implants were embedded in LR White acrylic resin (London Resin, Hampshire, England)
by a vacuum-impregnation technique, and the resin was thermally cured overnight at 50ºC to 60ºC.
Each embedded implant was sectioned parallel to its axis with a low-speed (approximately 100 rpm)
saw (Isomet, Buehler, Lake Bluff, IL), using a low-concentration diamond wafering blade (Buehler) and
an oil-based blade lubricant (Isocut, Buehler). Sectioning started from the coated end (base) to minimize
coating damage from the metal debris.17 The implants were sectioned in random order and were
ultrasonically cleaned in ethanol for 2 minutes. The specimens were then wet-ground with 1,000-grit
(18-µm) and 4,000-grit (5-µm) silicon carbide abrasive papers (Struers, Westlake, OH). Final polishing
was performed with 0.05-µm colloidal silica (OPS, Struers), and the specimens were again ultrasonically
cleaned in ethanol and carbon-coated for SEM examination. Using morphometric software and a
standardized magnification of 300×, the ceramic coating thickness was measured at four randomly
selected regions on each side of the cross-sectioned implant to yield eight measurements for each of the
three specimens.
Elemental analyses were performed by x-ray energy-dispersive spectroscopy (EDS) with the SEM,
using a Link eXL Microanalysis System with a silicon PentaFet detector and 7.6-µm beryllium window
(Oxford Analytical Instruments, High Wycombe, England). Prior to microanalysis, standard
characteristic x-ray spectra were acquired for Ca, P, Ti, Al, and V. During each experiment, EDS
analyses were obtained under standardized conditions at two or three sites in both the coating and
titanium alloy substrate. Raster scans were performed at 5,000× magnification, using an accelerating
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JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
voltage of 9 kV, a beam current of 3.0 nA, a live time of 200 counts per second, and a dead time of
approximately 30%. These conditions yielded a total number of at least 100,000 x-ray photon counts
from each site examined, which was considered necessary for an adequate elemental analysis.18
Sufficient x-ray analyses were performed to obtain quantitative information about the extent of elemental
interdiffusion at the coating-substrate interface resulting from the plasma-spraying process. To avoid the
possibility of spot overlapping and double counting during the EDS analyses, the depths of x-ray
penetration were calculated19 for the ceramic coating and the titanium alloy substrate. For HA and
Ti-6Al-4V, an accelerating voltage of 9 kV and the detection of Ka characteristic x-rays, the critical
distance between two spots to avoid overlapping interaction volumes is less than 0.5 µm.20
Consequently, the points selected for the EDS raster scans were at least 1 µm apart.
Results
Microstructures of Coating Surfaces. Scanning electron micrographs of representative surface regions
for the Integral and Bio-Vent implants are provided at the same magnification in Figs 1 and 2. All of the
implant cylinders examined had a relatively uniform HA coating at the surface, with microstructural
features consistent with plasma spraying: splat deposition sites; unmelted or incompletely melted starting
powder particles; porosities; and cracks.21 Figures 1 and 2 show that numerous unmelted or
incompletely melted starting powder particles with approximately spherical or equiaxed shapes were
found on the coating surfaces. It is evident that the scale of the microstructural features was much finer
for the Integral coatings.
Microstructures of Cross-Sectioned Implants. Representative photomicrographs of cross-sectioned
specimens are provided in Figs 3 and 4 for Integral and Bio-Vent implants, respectively. For all
cross-sectioned specimens of both implant products, the HA coating completely covered the Ti-6Al-4V
substrate, which was always observed to be roughened at the interface. Although there was no significant
difference in the coating thickness (Table 1) for the Bio-Vent (71.4 ± 24.3 µm) and Integral (72.1 ± 14.6
µm) implant specimens, using Student’s t test, the variability in coating thickness was typically less for
the Integral implants.
The surface cracks that were observed in the HA coatings (see Figs 1 and 2) did not extend to the
interface in any specimen. In all cross-sectioned specimens examined, the surface porosity was found to
be associated with areas of incomplete coverage or coalescence of the splat deposition regions. Few
pores were observed in the bulk coatings, and this minimal porosity might be the result of metallographic
specimen preparation.
Extensive observations of the interfacial regions revealed more intimate contact between the coating
and substrate for the Integral implants compared to the Bio-Vent implants. 20,22 Relative differences in
gap widths between the coating and substrate for the cross-sectioned specimens qualitatively suggested a
lower bond strength for the Bio-Vent implants, since all of these specimens were prepared by nominally
identical procedures. However, the observed interfacial gaps might have been related to specimen
preparation, in spite of the great care taken with these procedures (Larson FG, private communication,
1993).
In the cross-sectioned specimens, there were regions in the coatings that contained particles that
appeared as clusters. These particles correspond to the incompletely melted or unmelted particles
observed on the surfaces of the coatings (see Figs 1 and 2). Another type of particle was found in the
substrate near the interface for all the cross-sectioned specimens (see Figs 3 and 4). Elemental line scans
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indicated that these particles were aluminum-rich (Fig 5), and the intensities of the characteristic
aluminum and oxygen x-ray peaks in the EDS analyses were consistent with an Al2O3 composition (Fig
6). In addition, electron microprobe analyses (Model SX-50, Cameca, Paris, France) of the aluminum and
oxygen concentrations confirmed that the particles were Al2O3. The particles are assumed to be residual
alumina from grit-blasting the substrate surfaces, which is performed by manufacturers prior to plasma
spraying. Particular care with specimen preparation was required to resolve the aluminum-rich dark areas
as individual particles, which was not achieved in earlier research.20
Elemental Analyses. The EDS data demonstrated that titanium and aluminum diffused into the
coatings and calcium diffused into the substrates during plasma spraying. The concentration of calcium
in the substrates at a distance of approximately 1 µm from the interface was less than 1 weight percent,
while the concentration of phosphorus at this distance was below the EDS detection limit. The
concentration of titanium in the coatings at about 1 µm distance from the interface was approximately 2
to 4 weight percent, while the aluminum concentration was less than 2 weight percent. The concentration
of vanadium in the coating at this distance from the interface was below the EDS detection limit.
Detailed information about the extent of elemental interdiffusion in these implants is provided in another
study. 22
Discussion
During plasma spraying, the coating process is carried out by the deposition of melted starting powder
particles that splatter and very rapidly solidify onto the much cooler substrate. Consequently, these splat
deposition sites are the principal microstructural feature obtained with this technique.21 To achieve an
adherent coating, extensive and permanent contact of these solidified areas is necessary. 23 Because of
the complexity of the plasma-spraying process, there are several factors that can account for the HA
coating surface topography and the presence of unmelted or partially melted starting particles as shown
in Figs 1 and 2. These factors include the composition and temperature of the particles exiting the plasma
gun, the distance between the plasma gun and the substrate, the nature of the carrier gas, and the
deposition rate.24 Moreover, the plasma deposition of the HA coatings has proprietary details that differ
from those reported for other ceramic coatings (Burgess AV, Calcitek, private communication, 1993).
Because of the highly nonequilibrium nature of the plasma-spraying process, bioceramic coatings contain
multiple crystalline phases and an amorphous phase.11 Consequently, the general terminology of
calcium phosphate coatings, rather than HA coatings, is more appropriate for these dental implants.22
It is well known that surface porosity in bulk HA for some dental applications may not be detrimental
because such porosity can provide sites for bone ingrowth, osseointegration, and mechanical adhesion.
Although the present investigation cannot answer the question of whether surface porosity in the
plasma-sprayed coatings might harbor bacterial colonies in vivo,9,10 it can be seen that some pore sizes
in Figs 1 and 2 exceed the dimensions (less than 10 µm)25 of microbiota responsible for periodontal
infections and implant failure.26-28 Figures 1 and 2 further suggest that the potential ability of
plasma-sprayed coatings to harbor such bacteria might vary for different implant products and be
diminished with a finer-scale surface microtopography.
Another important consideration is that increased coating surface area for an implant, arising from
either surface porosity or a finer microstructural scale, could lead to greater coating resorption or to an
increased amount of metal ions released from the underlying titanium alloy substrate.29,30 The coating
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thickness range observed for both implants was comparable to the 50-µm value generally accepted as
optimum for providing adequate coating strength and preventing slow release of metal ions in vivo from
the substrate.6
Figures 1 and 2 also show cracks in the coatings, which most probably formed because of the high
internal stresses developed as a result of the very rapid cooling rates characteristic of plasma
deposition.23 The presence of such cracks might result in appreciably lower strength and fracture
toughness, as well as eventual failure, for the coatings. The apparent layers parallel to the interface in the
coatings, which can be seen in Figs 3 and 4, might correspond to successive splat deposition layers
during a single step of plasma spraying or to successive plasma-spraying steps where the coating was
applied layer by layer. The present microstructural observations do not permit an unambiguous choice
between these two alternative interpretations, and such information about the plasma-spraying processes
is proprietary with the manufacturers.
The observation that calcium diffused across the interface into the Ti-6Al-4V substrates for both
HA-coated implants is at variance with previous results by Ducheyne et al13 and Filiaggi et al,16 who
found that diffusion of phosphorus rather than calcium occurred from the HA coating into the titanium or
Ti-6Al-4V substrate, respectively. While the diffusion of phosphorus rather than calcium might be
expected because of the larger ionic radius for the latter, 16 the present result is attributed to the use of
commercial endosseous implants instead of laboratory specimens and to differing localized
temperature-time conditions during the coating process. For example, Ducheyne et al13 analyzed HA
coatings that had been deposited by electrophoresis and sintered for 1 hour at 950ºC, whereas the
plasma-sprayed specimens used by Filiaggi et al16 had a modified short-bar configuration for the
evaluation of interfacial fracture toughness. The decreased diffusion of titanium into the HA coatings in
the present study compared to that reported by Ducheyne et al13 is attributed to the postdeposition heat
treatment used in their study; Filiaggi et al16 did not observe significant titanium diffusion from the
Ti-6Al-4V substrate into their plasma-sprayed coatings. Although details about the plasma spraying for
commercial HA implant coatings are proprietary, the manufacturers consider that deposition is a
relatively low-temperature process (Larson FG, private communication, 1993).
The very limited diffusion of titanium into the HA coatings would not be expected to cause any
biologic problems because this element is considered to be highly biocompatible. While the long-term
consequences of titanium in hard and soft tissues are unknown, the bioceramic coating acts as a shield to
drastically reduce slow ion release from the Ti-6Al-4V substrate. 30 The interdiffusion of titanium and
calcium during plasma spraying may provide a chemical component to the coating-substrate bond
strength. Filiaggi et al16 have suggested that the phosphorus diffusion from their plasma-sprayed
coatings into the Ti-6Al-4V substrate or the titanium oxide layer should provide some chemical bonding.
The coating-substrate bond is considered to be principally mechanical,16 and metal surface roughening
by alumina grit blasting prior to plasma spraying the bioceramic is employed by manufacturers to
promote coating adherence (Larson FG, private communication, 1993).
Conclusions
Both brands of implants had HA coatings with microstructural features expected from plasma spraying.
The microstructural scale for the Integral implants was much finer because of differences in the
proprietary plasma-spraying processes. Examination of the cross-sectioned specimens suggested that the
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JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
Integral implants exhibited more intimately adapted and adherent coatings, although specimen
preparation procedures may have contributed to the interfacial gaps observed. In cross-section, the bulk
coatings for both implants had minimal porosity. Aluminum oxide particles observed near the interface
were assumed to arise from the use of this abrasive by both manufacturers for substrate surface
preparation prior to plasma spraying. Elemental analyses at the coating-substrate interface demonstrated
that limited interdiffusion of titanium and calcium occurred during the plasma spraying. This
interdiffusion may provide a chemical component to the coating-substrate bond strength.
Acknowledgments
The authors are grateful to Calcitek and Dentsply Implant Division for contributing the implants used
in this study. Professor Dennis W. Foreman provided assistance in calculating the interaction volume
between the specimen and primary electron beam during the elemental microanalysis. The authors also
wish to thank Floyd G. Larson, Pacific Materials and Interfaces, for helpful discussions on the
manufacturing of HA-coated dental implants and Michael C. Comerford, Microscopic and Chemical
Analysis Research Center, Department of Geological Sciences, for assistance with the electron
microprobe analysis. Support was provided by a research grant from Ohio State University College of
Dentistry.
Eser Tufekci
William A. Brantley
John C. Mitchell
Edwin A. McGlumphy
Footnotes 6
Associate Professor, Section of Restorative
Dentistry, Prosthodontics and Endodontics, Ohio
State University, Columbus, Ohio.
FIGURES
Figure 1
Fig. 1 Scanning electron micrograph of a surface region for a representative Integral implant
(original magnification × 1,000, bar = 10 µm). The photomicrographs in Figs 1 to 4 are
secondary electron images.
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JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
Figure 2
Fig. 2 Scanning electron micrograph of a surface region for a representative Bio-Vent implant
(original magnification × 1,000, bar = 10 µm).
Figure 3
Fig. 3 Scanning electron micrograph of a cross-sectioned Integral implant. The coating (C) is in
the center of the figure, and the titanium alloy substrate (T) and the aluminum-rich dark regions
(A) described in the text are in the top portion of the figure (original magnification × 1,000, bar =
10 µm).
Figures 8
JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
Figure 4
Fig. 4 Scanning electron micrograph of a cross-sectioned Bio-Vent implant. The coating (C) is
in the center of the figure, and the titanium alloy substrate (T) is at the right side. Alumina
particles (A) embedded in the substrate are conspicuous at the right edge of the coating
(original magnification × 1,000, bar = 10 µm).
Figures 9
JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
Figure 5
Figures 10
JOMI on CD-ROM (1997 © Quintessence Pub. Co.), 1997 Vol. 12, No. 1 (25 - 31): Microstructures of Plasma-Sprayed Hydroxyapatite-Coated Ti-6A
Figure 6
Fig. 6 Intensities of characteristic x-rays for the EDS analysis of the aluminum-rich particle in
Fig 5. The aluminum and oxygen peaks are consistent with an Al2O3 composition. The carbon
peak is the result of the conducting coating on the specimen, and the sodium peak is attributed
to the presence of minor surface contamination.
TABLES
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Table 1
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the mechanical strengths and histological profiles of titanium implant materials. J Biomed Mater Res
1987;21:1395–1414.
3. de Lange GL, Donath K. Interface between bone tissue and implants of solid hydroxyapatite or hydroxyapatite
coated titanium implants. Biomaterials 1989;10:121–125.
4. Cook SD, Thomas KA, Kay JF, Jarcho M. Hydroxyapatite-coated titanium for orthopedic implant applications.
Clin Orthop 1988;232:225–243.
5. Soballe K, Hansen ES, Brockstedt RH, Pederson CM, Bunger C. Hydroxyapatite coating enhances fixation of
porous coated implants. A comparison in dogs between press fit and noninterference fit. Acta Orthop Scand
1990;61:299–306.
6. de Groot K, Geesink R, Klein CPAT, Serekian P. Plasma sprayed coatings of hydroxylapatite. J Biomed Mater
Res 1987;21:1375–1381.
7. English CE. Cylindrical implants. Calif Dent Assoc J 1988;16:17–38.
8. Kent J, Finger I, Larsen H. Biointegrated hydroxylapatite-coated dental implants: 5-year clinical observations. J
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