d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305

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Surface characterization of zirconia dental implants

S. Zinelis a , A. Thomas b , K. Syres b , N. Silikas c , G. Eliades a,∗

a Department of Biomaterials, University of Athens, Greece
b School of Physics and Astronomy, Photon Science Institute, University of Manchester, UK
c Biomaterials Unit, University of Manchester, UK

a r t i c l e i n f o a b s t r a c t

Article history: Objectives. The aim of the study was to characterize the chemical composition, microstruc-
Received 27 May 2009 ture and roughness of two commercially available zirconia dental implants (WhiteSky and
Received in revised form Zit-Z).
27 September 2009 Methods. The chemical composition of the cervical collar and threaded root parts of the
Accepted 17 November 2009 implants (n = 2) were studied by XPS and HV-EDX. LV-SEM was used for morphological
assessment, Raman microanalysis for microstructural characterization and optical pro-
filometry for surface roughness measurements. XRD, HV-EDX and Raman microanalysis
Keywords: of bulk regions (longitudinal sections) were used as reference.
Zirconia dental implants Results. XPS showed the presence of C, O, Zr and Y (collar) plus Al (root) at implant surfaces.
Surface analysis More C (10–26 at%) and a lower Al/Zr ratio were found in WhiteSky (1.05 vs 1.26 in Zit-Z). Zr,
XPS Y and Al were detected in single, fully oxidized states. The same elements, plus Hf, were
Raman microanalysis identified by HV-EDX at bulk and surface regions, with a Al/Zr ratio higher in WhiteSky
SEM/EDX (0.17 vs 0.09 in Zit-Z). Na, K and Cl contaminants were traced at implant root parts by both
Optical profilometry methods. XRD analysis of cross-sectioned specimens revealed the presence of monoclinic
and tetragonal zirconia along with cubic yttria phases. Raman microanalysis showed that
the monoclinic zirconia volume fraction was higher at root surfaces than the collar. No
monoclinic phase was found at bulk regions. Significantly higher Sa and Sq values were
recorded in WhiteSky than Zit-Z, whereas Zit-Z showed higher Rt value.
Significance. The differences found between the implants in the extent of carbon contami-
nation, residual alumina content, tetragonal to monoclinic ZrO2 phase transformation and
3D-roughness parameters may contribute to a substantial differentiation in the cellular and
tissue response.
© 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

matory response and better stabilization of soft-tissues in

1. Introduction
Tetragonal stabilized ZrO2 , with the addition of 3 mol%
Y2 O3 (3Y-TZP) has long been considered as a strong, tough,
wear-resistant and osseoconductive ceramic suitable for
stress-bearing implantable applications [1,2]. The less inflam-
contact with zirconia [3,4], the lower plaque retention capac-
ity and higher affinity to ostoeblasts [5–7] along with the more
aesthetic tooth-like colour have made 3Y-TZP a viable alterna-
tive to titanium implants.
Already, several zirconia implants have been introduced
with proven efficacy in animal studies [8,9]. However,

∗
Corresponding author at: Department of Biomaterials, University of Athens, School of Dentistry, 2 Thivon Str-Goudi, 115 27 Athens,
Greece. Tel.: +30 210 7461101; fax: +30 210 7461306.
E-mail address: geliad@dent.uoa.gr (G. Eliades).
0109-5641/$ – see front matter © 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2009.11.079
296 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305
long-term human trials to establish their clinical success are
still missing [10].
From the material standpoint, concerns have been
expressed on the low temperature degradation of the tetrag-
onal to monoclinic ZrO2 phase, that has been associated with
in-service failures of orthopaedic implants [11,12]. Treatments
to avoid or reverse such transformations have been advocated
during manufacturing or sterilization [13]. Moreover, it has
been shown that the osseointegration capacity of machined
ZrO2 surfaces is substantially increased after modification
by Al2 O3 sandblasting [14]. Although such techniques have
already been adopted in some products, there is lack of infor-
mation on the surface chemistry, structure and morphology
of currently commercially available ZrO2 dental implants
that would facilitate understanding of the implant–bone
interactions and the bone augmentation mechanisms
involved.
The aim of the present study was to investigate the surface
chemistry, morphology and structure of two commercially
available zirconia implants. The testing hypothesis was that
significant differences exist in these properties between the
two implants.
2. Materials and methods
The products tested were WhiteSky (Ø: 3.5 mm, l: 12 mm,
lot 59235, Bredent Medical, Senden, Germany) and Zit-Z (Ø:
3.5 mm, l: 13 mm, lot 49744, Ziterion, Uffenheim, Germany).
Five specimens from each product were subjected to the fol-
lowing testing procedures:
2.1. X-ray photoelectron spectroscopy (XPS)
The samples as received (n = 2) were placed in the ultra-high
vacuum chamber of an X-ray photoelectron spectrome-
ter (Scienta 300 ESCA system, NCESS, Cheshire, UK). Two
regions, one at the cervical collar and the other at the
threaded root portion, were located on each implant and
analyzed under the following conditions: Al Ka (1486.7 eV)
monochromated rotating anode, 14 kV accelerating voltage,
0.2 A current emission, 2.8 kW maximum power, 10−9 mbar
pressure, ∼90◦ electron take-off angle, 0.30 eV energy reso-
lution and 6 mm × 0.5 mm sampling area. An electron flood
gun operated at 4 eV was used for charge compensation.
Energy calibration was performed based on Ag3d5/2 peak stan-
dard. Survey scans (150 eV pass energy) were taken from
each region to identify the elements present on the surface.
Then, high resolution narrow scans (150 eV pass energy) were
recorded over the predominant peaks and the elemental bind-
ing states were determined. All spectra were aligned on the
binding energy scale to the C 1s peak arising from adven-
titious hydrocarbons (–CH2 –, 285 eV BE). The core level data
were analyzed using the CASA XPS software package. A Shirley
background was subtracted from the data and 80:20 Gaus-
sian:Lorenzian peaks fitted to give binding energy positions.
The fitted peak areas in conjunction with relative inten-
sity factors allowed the elemental ratios at the surface to
be quantified. The depth of analysis was estimated as to
3 nm.
2.2. Low-vacuum scanning electron microscopy and
high vacuum X-ray energy dispersive microanalysis
(LV-SEM/HV-EDX)
The same specimens analyzed by XPS were subjected to
LV-SEM imaging. Secondary electron images were acquired
employing a large field detector (LFD) attached to a SEM
unit (Quanta 200, FEI, Hillsboro, OR, USA) operated at 30 kV
accelerating voltage, 90 ␮A beam current, 1 Torr pressure
(without electron conductive coating to avoid masking off
microstructural features) at 40×, 300×, 600× and 2400×
magnifications.
The elemental composition of cervical collar, threaded
root and bulk regions (the latter prepared for XRD analy-
sis as described below) of each implant were determined
by HV-EDX analysis (this technique provides better accuracy
in quantitative determinations than LV-EDX). All the spec-
imens were coated with a thin layer of conductive carbon
in a sputter-coating unit (SCD 004 Sputter-Coater with OCD
30 attachment, Bal-Tec, Vaduz, Liechtenstein). EDX analy-
sis was performed using a liquid N2 -cooled Si(Li) detector
with super ultra-thin Be window (Sapphire SUTW+ CDU,
EDAX Int, Mahwah, NJ, USA) attached to the SEM unit under
the following conditions: 30 kV energy range, 10−6 Torr pres-
sure, 110 ␮A beam current, 128 eV resolution, 250 s acquisition
time, 210 ␮m × 210 ␮m sampling window and 28–34% detector
dead time. The depth of analysis was estimated as to 1 ␮m.
The quantitative analysis was performed in non-standard
mode using ZAF and coating corrections employing Gene-
sis v. 5.2 software (EDAX, Int). Elemental mapping of regions
of interest was based on compositional backscattered elec-
tron images, obtained with a solid-state detector (SSD) at
the same conditions as above, but at 15 kV accelerating
voltage.
2.3. Raman microanalysis
The cervical collar, threaded root parts bulk regions (pre-
pared for XRD analysis as described below) of the implants
(n = 2) were analyzed by Raman microscopy to identify and
map the distribution of the tetragonal (145 and 262 cm−1
Raman shift) and monoclinic (180 and 190 cm−1 Raman
shift) ZrO2 phases at the surface region [15]. A Raman
microscope was used (LabRAM Aramis, Horiba Jobin-Yvon,
Villeneuve d’Ascq, France) operated under the following
conditions: Ar laser (532 nm), 10 mW power at sample,
50× LWD objective, 1800 grit/mm grating, 1000 ␮m confo-
cal hole (defocused mode), 100 ␮m slit, 10 s acquisition.
Three regions were randomly located at each implant sur-
face location (collar/root) with the optical system of the
microscope (10× optical objective) and analyzed. For map-
ping of the monoclinic ZrO2 phase, 20 ␮m × 35 ␮m areas
were selected and scanned at 5 ␮m steps and 5 s acquisition
time.
From the net peak height intensities of the monoclinic and
tetragonal ZrO2 phases, the percentage volume of the mono-
clinic phase (Vm %) was calculated according to the equation:
Vm % = {I180 + I190 /0.97(I145 + I262 ) + I180 + I190 } × 100, where I the
net peak height intensities at the corresponding Raman shifts
[15].
 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305
2.4. X-ray diffraction (XRD)
In order to examine the presence of the tetragonal and mon-
oclinic ZrO2 phases in the entire implant, one specimen from
each implant was embedded in epoxy resin and sectioned at
a longitudinal direction using a microtome under continuous
water cooling. The specimens were ground to a smooth sur-
face using SiC paper up to 1200 grit size, polished with a 3 ␮m
diamond paste and ultrasonically cleaned in a distilled water
bath for 3 min. The sections were studied in an X-ray diffrac-
tometer (D8 Focus, Bruker AXS, Karlsruhe, Germany) under the
following conditions: CuKa anode, 40 kV accelerating voltage,
40 mA beam current, 20–90◦ 2 range, 0.02◦ step, 2 s exposure
per step. The identification of phases was based on the ICSD
database [16].
2.5. Optical profilometry
The 3D-surface roughness parameters of the threaded parts of
the implants (n = 2) were evaluated by optical profilometry. The
area between two successive implant threads was analyzed
by an optical profiler (NT 1100, Veeco, S. Barbara, CA, USA)
equipped with Michelson/Mirau interferometric objectives
at 10–100× magnifications. Quantification of the 3D-surface
roughness parameters Sa (arithmetic mean deviation), Sq
(root mean square deviation), and Rt (maximum peak to val-
Fig. 1 – XPS spectra of implant surfaces.(a) Survey spectrum of WhiteSky; (b) Survey spectrum of Zit-Z; High resolution
spectra of Zr 3d (c) and Y 3d peaks (d).
297
ley height) was performed by Veeco-Vision software at 40×
magnification (160 ␮m × 120 ␮m).
2.6. Statistical analysis
The results of elemental at% obtained from XPS and EDX were
subjected to a two-way ANOVA (implant type and region as
independent variables, and at% per element as dependent
variable), whereas a two-way ANOVA was used for Vm % com-
parisons (implant type and region as independent variables).
A Tukey’s test was used for pairwise multiple comparisons.
Finally, the differences in the roughness parameters between
the implants were evaluated by a t-test. In all comparisons
a 95% confidence level was used (˛: 0.05). Statistical analysis
was performed by SigmaStat software (Jandel, St. Raphael, CA,
USA).
3. Results
3.1. XPS
Fig. 1(a and b) shows representative survey XPS spectra of the
implants taken from cervical collar and threaded root regions.
The elements identified were C, O, Al, Zr and Y. The results of
the XPS elemental atomic percentage (at%) are listed in Table 1.
298 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305

Fig. 2 – Low-vacuum secondary electron images of the implant surfaces. WhiteSky: (a) Low magnification view (40×, bar:
1 mm); (b) cervical collar-threaded root transitional zone (300×, bar: 100 ␮m); (c) threaded root (600×, bar: 50 ␮m); (d)
threaded root at high magnification (2400×, bar: 20 ␮m). Zit-Z: (e) Low magnification view (40×, bar: 1 mm); (f) cervical
collar-threaded root transitional zone (300×, bar: 100 ␮m); (g) threaded root (600×, bar: 50 ␮m); (h) threaded root at high
magnification (2400×, bar: 20 ␮m).
 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305 299

Table 1 – XPS elemental composition of the Zirconia implant surfaces (mean and sd in parentheses)* .
Element (%) WhiteSky Zit-Z

Collar Threaded root Collar Threaded root

a,b,c a b
C (1s) 76.00 (3.18) 53.80 (1.88) 49.30 (1.62) 43.30c (1.94)
O (1s) 17.70d,e,f (1.44) 32.50d,g,h (0.84) 38.90e,g (1.78) 41.20f,h (1.02)
Zr (3d) 5.90i (0.12) 6.50j (0.44) 11.22i,j,k (0.56) 6.60k (0.86)
Y (3d) 0.40l (0.06) 0.40 (0.08) 0.58 (0.1) 0.70l (0.08)
Al (2s) – 6.80 (0.80) – 8.20 (0.64)
∗
Same letters indicate mean values with statistically significant differences per element between implant groups (p < 0.05).

The implant surfaces have similar qualitative composition.
Al was identified only at threaded root regions. WhiteSky
demonstrated more C contamination and less O content at
the cervical collar. The highest Zr content was found at Zit-Z
collar. The XPS Y/Zr atomic ratios, as derived from the data
listed in Table 1, ranged from 0.05 to 0.07 (p > 0.05), with the
exception of Zit-Z collar, where the highest value of 0.15 was
recorded (p < 0.05). The Al/Zr atomic ratios for WhiteSky and
Zit-Z were 1.05 and 1.27 respectively (p < 0.05). The Zr 3d and
Y 3d peaks showed only one doublet arising from 3d5/2 and

Fig. 3 – High-vacuum EDX spectra of the implants tested along with the elemental distributions of the dispersed phases at
threaded root regions. (a) Spectra of cervical collar for WhiteSky; (b) Spectra of threaded root for Zit-Z; Al X-ray maps (green)
imaged onto the corresponding compositional backscattered electron images for WhiteSky (c) and Zit-Z (d); X-ray maps of
Al–O–C for WhiteSky (e) and of Al–Na–K–C for Zit-Z (f) imaged onto the corresponding backscattered electron images.
300 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305
Table 2 – EDX elemental composition of the Zirconia implants (mean and sd in parentheses)* .
Element (%) WhiteSky
Bulk Collar Threaded Root
O (K) 64.55 (0.85) 68.10 (0.83)
Zr (L) 31.50 (0.80) 28.12 (0.87)
Y (L) 3.49 (0.24) 3.29 (0.32)
Hf (L) 0.46 (0.14) 0.48 (0.04)
Al (K) – –
∗
Same letters indicate mean values with statistically significant differences per element between implant groups (p < 0.05).
3d3/2 spin orbit splitting, indicating that Zr and Y exist in one
oxidation state in the implants (Fig. 1c and d). The binding
energy of the Zr 3d5/2 peak at 182.4 eV corresponds to ZrO2 ,
whereas that of theY 3d5/2 peak at 156.8 eV to Y2 O3 . For Al, the
binding energy of the Al 2p peak at 74.68 eV corresponds to
Al2 O3 . Traces of Na were also identified (Na 1s at 1023 eV and
Na Auger at 499 eV) in both implants.
3.2. LV-SEM/HV-EDX
Fig. 2(a and e) illustrates low-vacuum secondary electron
images of the threaded roots of the implant surfaces at low
magnification, which revealed distinct morphological differ-
ences. WhiteSky demonstrated a double thread self-cutting
design with a longitudinal retentive groove, whereas Zit-Z a
cylindrical screw design. Fig. 2(b and f) exhibits the transitional
zone between the cervical collar and the threaded root part of
the implants. The cervical collars showed horizontal machin-
ing serrations, more pronounced in Zit-Z. The transition of
the collar to the rough threaded root part was more clearly
defined in WhiteSky. In Zit-Z the machining tracks were vis-
ible even in the roughened threaded root region (Fig. 2c and
g). Both implants showed a grainy texture at the root regions.
However, the size of the grainy domains was much smaller in
Zit-Z (Fig. 2d and h).
The HV-EDX analysis showed that the implants were com-
posed of O, Hf, Y, and Zr. On the threaded root regions, Al was
identified as well (Fig. 3a and b). The quantitative results are
summarized in Table 2. A significant interaction was found
among the independent variables. Comparison between the
implants per same region showed that Zit-Z exhibited the
lowest O and the highest Zr content at the threaded root part.
The EDX Y/Zr atomic ratios as derived from the results pre-
sented in Table 2 ranged from 0.10 to 0.12 (p > 0.05), whereas
the Al/Zr atomic ratios were 0.17 (WhiteSky) and 0.09 (Zit-Z,
p < 0.05). Elemental mapping showed that the Al distribution
followed the dark regions (low atomic number regions) of the
backscattered images (Fig. 3c and d). At some of these regions
C, Na, K and Cl contaminants were mapped (Fig. 3e and f).
3.3. Raman microanalysis
Raman spectra taken from cervical collar and the treaded root
parts are illustrated in Fig. 4(a–d). The low intensity peaks at
180 and 190 cm−1 Raman shift correspond to the monoclinic
ZrO2 phase and the high intensity peaks at 145 and 262 cm−1
Raman shift to the tetragonal ZrO2 phase. The threaded parts
exhibited more intense monoclinic peaks in both implants.
Zit-Z
Bulk Collar Threaded Root
a
72.28 (1.58) 64.90 (0.66) 61.99 (1.28) 54.78a (4.27)
21.51b (1.58) 30.97 (0.83) 33.57 (1.22) 37.45b (3.70)
2.37c (0.14) 3.40 (0.17) 3.88 (0.38) 3.38c (0.09)
0.25d (0.03) 0.47 (0.03) 0.55 (0.06) 1.08d (0.38)
3.58 (0.06) – – 3.30 (0.12)
The results of the percentage volume of the monoclinic phase
(Vm %) are presented in Table 3. No interaction was found
between the independent variables. The threaded root parts
demonstrated the highest Vm % (p = 0.05). No monoclinic phase
was detected at bulk regions. Raman mapping showed that at
cervical collars the monoclinic phase distribution was related
to deep machining grooves, whereas a more uniform distribu-
tion was found at the treaded parts (Fig. 4e and f).
3.4. X-ray diffraction (XRD)
Representative XRD graphs are given in Fig. 5(a and b). The
monoclinic ZrO2 phase was clearly identified (2: 28.2◦ ) along
with the tetragonal ZrO2 (2: 30.2◦ ) and cubic Y2 O3 (2: 29.1◦ )
phases. The presence of the latter phase was verified by the
second peak as well (2: 48.5◦ ). No cubic zirconia phase was
identified.
3.5. Optical profilometry
3D-topometric images of the threaded root regions are given
in Fig. 6(a–c).
WhiteSky demonstrated a rougher surface texture com-
pared with Zit-Z. The machining tracks were apparent in the
root part of Zit-Z. Fig. 6(c) illustrates a top-view image of
the surface between two successive threads after automatic
plane subtraction; the latter was used for calculation of the
surface roughness parameters. The surface roughness param-
eters calculated at 40× are summarized in Table 4. WhiteSky
demonstrated significantly higher roughness parameters than
Zit-Z (p < 0.05).
4. Discussion
The results of the present study confirmed the testing hypoth-
esis, that significant differences exist between the implants in
the properties tested.
HV-EDX analysis of bulk sectioned specimens confirmed
that in both implants yttria-stabilized zirconia was used as
raw material with a composition complying with the lim-
its described for biomedical applications (4.5–5.5% Y2 O3 , <5%
HfO2 , ZrO2 + Y2 O3 + HfO2 ∼99%) [17,18]. According to the man-
ufacturers, sintering of the implants was performed by hot
isostatic pressure (HIP). XRD revealed that a fraction of the
monoclinic ZrO2 phase existed in the implants along with the
predominating tetragonal ZrO2 phase. However, since XRD as
applied, lacks of lateral resolution, it is unclear whether the
 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305 301

Fig. 4 – Raman microanalysis of the implant surfaces. Spectra taken at 3 different locations at cervical collar (a: WhiteSky, c:
Zit-Z) and threaded root locations (b: WhiteSky, d: Zit-Z). Mapping of the monoclinic ZrO2 phase distribution at cervical
collar (e) and threaded root regions (f) for WhiteSky implant.
302 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305

Table 3 – Percentage of the monoclinic ZrO2 volume

(Vm %, mean and sd in parentheses)* .
Vm % WhiteSky Zit-Z
Collar 1.97b (1.82) 3.00c (0.50)
Threaded root 4.10a (3.61) 6.27c (0.81)
Bulk 0a,b 0c
∗
Same letters indicate mean values with statistically significant
differences (p < 0.05).

These values may imply that the residual Al2 O3 particles in

Zit-Z are aggregated in a thinner superficial layer. The highest
Y/Zr XPS atomic ratio found at Zit-Z threaded root part may
imply regional yttria segregation. Although the role of resid-
ual Al2 O3 on implant surfaces is still a matter of controversy,
animal studies have shown that these particles do not affect
the osseointegration pattern [20]. Nevertheless, since the low
content of residual Al2 O3 particles on implant root surfaces
demonstrates a randomly dispersed pattern, it is quite difficult
to conclude on a positive or negative effect from low magni-
fication histomorphometric images in the absence of Al2 O3
particles from the field of view.
No Hf was detected by XPS, implying that Hf compounds
do not occupy surface sites. Zr and Y were found as ZrO2
and Y2 O3 in one, fully oxidized state that complies with ISO
and ASTM standards for ceramic surgical implants based
Fig. 5 – XRD graphs of WhiteSky (a) and Zit-Z (b) implants.
on Y-TZP [17,18]. WhiteSky showed more carbon contamina-
t: tetragonal ZrO2 , m: monoclinic ZrO2 and c: cubic Y2 O3
tion, possibly related to the cleaning procedures after surface
phases.
treatments. It is not known if the increased level of carbon
contamination on zirconia surfaces affects the protein and
cell adsorption phenomena, as documented for Ti surfaces
monoclinic phase detected corresponded to surface or bulk
[21]. The presence of Na, K and Cl contaminants, occasionally
regions. Moreover, it is not known if the sectioning proce-
detected by XPS and EDX on implant surfaces, may be residues
dure created stresses that contributed to monoclinic phase
of proprietary cleaning treatments performed after sandblast-
formation [19]. The same observations may apply for the
ing, for which no information is given. The biological role of
cubic Y2 O3 phase. Raman microspectroscopy showed lack of
these contaminants is undefined [22].
monoclinic zirconia phase at bulk regions. Although Raman
The Raman analysis of the collar and treaded implant
microanalysis does not provide information for the entire
surfaces showed the presence of the weak monoclinic ZrO2
implant section, the randomly analyzed regions may be con-
phase in both implants. The low laser energy used on tar-
sidered representative of the bulk implant microstructure. The
get (10 mW) and the short spectra acquisition time (10 s max)
absence of monoclinic phase at bulk regions implies that the
did not affect the phase composition, due to overheating, as
raw materials used were free of monoclinic surface and that
confirmed by pilot measurements. Since the implants were
the sectioning technique employed did not induce this phase.
analyzed as received, it can be concluded that the mono-
The surface chemistry of the implants showed substantial
clinic phase was developed either during implant machining
differences from bulk. XPS and EDX documented the presence
or/and sandblasting, considering the absence of this phase
of Al as Al2 O3 on the threaded root part. As per manufac-
from raw materials (bulk region). The more uniform pattern
turers’ information these surfaces were alumina sandblasted,
and the higher extent of the Vm % found on the threaded sur-
but no further details are given for the procedure. Sandblast-
faces implies that sandblasting induced more stresses that
ing with Al2 O3 , usually at 5 atm with 250 ␮m size particles,
has been described as a method to increase implant macro-
roughness, that when combined with acid-etching (to increase
micro-roughness), leads to enhanced bone apposition and Table 4 – The 3D-roughness parameters of the threaded
increased torque removal strength [14]. A 3–4 at% Al was found root implant regions (mean and sd in parentheses)* .
at the uppermost ∼1 ␮m surface layer of the root parts of the
Parameters (␮m) WhiteSky Zit-Z
implants by EDX, while a 6–8 at% Al by XPS. The highest values
Sa 1.31 (0.06) 0.66 (0.05)
of the latter should be assigned to the smaller probing depth
Sq 1.58 (0.03) 0.85 (0.04)
of XPS (∼3 nm) that is much more sensitive to surface treat-
Rt 10.95 (2.10) 25.72 (5.42)
ments. The Al/Zr atomic ratios of the implants after XPS were
∗
All mean values showed statistically significant differences
1.05 for WhiteSky and 1.26 for Zit-Z. The corresponding ratios,
between implants (p < 0.05).
though, after EDX were 0.17 for WhiteSky and 0.09 for Zit-Z.
 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305 303

Fig. 6 – 3D-optical profilometric images of threaded root regions of WhiteSky (a, 100X) and Zit-Z (b, 100×). For calculation of
the surface roughness parameters, the top-view images were subjected to automatic plane subtraction (c: WhiteSky).

destabilized tetragonal phase more aggressively than machin-
ing. The tetragonal to monoclinic ZrO2 phase transformation
is followed by a 4–6% increase in volume that generates
stress fields, which are associated with the development of
defects, like surface and subsurface cracking, grain pull-out
and damage, that may affect load bearing interfaces like
the bone–implant interface [23]. The Vm % found on implant
surfaces was quite low (0–7.2%). However, studies on trans-
formation kinetic parameters have shown that the growth of
initial fraction of monoclinic phase further affects the surface
degradation mechanism, despite that formation of new mon-
oclinic nuclei is considered as the predominant effect [24]. It
is quite interesting that no requirement on the pre-existing
monoclinic phase content is listed in the relevant ISO specifi-
cation [17].
The Raman analysis as performed in the present study,
probed only the surface layer, extending to a depth of a few zir-
conia grain diameters. However, the importance of this zone
is high, since a low percentage of monoclinic phase extending
to a depth of some microns has been found to severely reduce
the strength of Y-TZP [25].
Further studies employing confocal Raman microanalysis
could provide important information regarding the in-depth
extent of the tetragonal to monoclinic ZrO2 phase trans-
formation and the distribution of the stresses developed
[23].
Dental implants are not similar to orthopaedic implants,
where many problems have been encountered from the low
temperature degradation and transformation of the tetrago-
nal to monoclinic ZrO2 phase, that resulted in grain pull-out
and catastrophic 3-body abrasive wear of the zirconia articu-
lating surfaces (hip and acetabular cap) [12,26]. Nevertheless,
osseointegration with a superficial zirconia zone rich in mono-
clinic phase could create subsurface cracking under functional
loading due to the great interfacial elastic modulus mismatch
with bone. Additionally, in-service development of the mono-
clinic zone, starting from the surface and progressing into the
material bulk, might further contribute to bulk and interfacial
problems. The exact mechanism of tetragonal to monoclinic
ZrO2 transformation in aqueous medium is unknown. Three
mechanisms have been proposed so far [11]: First is the cor-
rosion mechanism, where the transformation proceeds from
the hydrolytic degradation of the Zr–O–Zr bonds at the crack
tips leading to formation of Zr–OH, that relieve the strains
stabilizing the tetragonal phase, while at the same time OH-
groups diffuse into the lattice to occupy oxygen vacancies. It
should be mentioned that the addition of Y3+ in Zr4+ sites of
Y-TZP creates oxygen vacancies due to establishment of Zr–O
304 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 295–305
charge density differences [27]. Second, the destabilization
mechanism, concerns interaction of OH− groups with Y2 O3
and formation of hydroxylated yttria compounds (i.e. YO(OH),
Y(OH)3 ) that destabilize the tetragonal phase. Finally, the
stress induced transformation mechanism applies for cases
of water vapour stress development (i.e. during autoclave ster-
ilization) that leads to Y(OH)3 formation and subsequently to
monoclinic phase formation. As most zirconia dental implants
are sterilized by ␥-rays, the first and second mechanisms
could potentially apply. Retrieval analysis of zirconia dental
implants would greatly assist in understanding the possible
implication of the monoclinic phase to the failure mecha-
nisms.
Of particular interest for osseointegration is the surface
topography of the implants, especially within the areas con-
fined by single threads that are representative of the implants’
microtopography. Measurements at this region are quite chal-
lenging since the exaggerated form of the threaded structure
provides physical limitations to several stylus-type instru-
ments (i.e. stylus profilometers, AFM scanners, etc.) [28]. The
optical profiler used in the present study, operating in non-
contact mode, overwhelmed these limitations. Although none
of the roughness parameters has been directly related to
bone response, height descriptors (like Ra, Rq, Rz, Rt, etc.)
are more frequently used to characterize implant surfaces.
In addition, 3D-roughness parameters are considered more
important than the 2D-analogues, since the surface texture
anisotropy that modifies cell response is taken into account
in the former, the latter providing information only for in-
line measurements [28]. The Sa and Sq values of WhiteSky
were within the range of the values previously reported for
a sandblasted and acid-etched cpTi implant [14], whereas
the corresponding values of Zit-Z were almost half of the
above. The differences in the surface roughness between the
implants tested may be attributed to different sandblasting
and etching conditions after machining. The lower Sa and
Sq values of Zit-Z comply with the SEM and 3D-topometric
images, where the machining tracks were detectable even on
the sandblasted surfaces. Rt, being a single value per surface
scan, does not represent a statistical finding of the surface but
rather an indication of the maximum vertical surface variance.
Increased surface roughness of sandblasted and acid-etched
zirconia implants has been associated with increased removal
torque strength and bone stability, despite that no differences
in osseointegration have been recorded in histomorphometric
studies [14]. Although no comparative studies are available for
these implants, it has long been recognized that roughness is a
critical factor for a strong bone–implant augmentation [29,30].
The results of the present study show that signifi-
cant differences exist in the surface chemistry, structure
and roughness of the implants tested, although both were
based on the same composition and received similar sur-
face treatments. The differences found in the extent of
carbon contamination, residual alumina content, tetragonal
to monoclinic ZrO2 phase transformation and 3D-roughness
parameters may contribute to a substantial differentiation in
the cellular and tissue response. Nevertheless, the significance
of these properties in the success of Y-TZP dental implants can
be verified only by controlled long-term clinical studies that
currently are not available [10].
Acknowledgements
The study was supported by the ELKE 70/4/5768 research fund
from the National and Kapodistrian University of Athens. The
support provided by Dr. E. Lancelot (Raman microanalysis), Dr.
H. Stadler (optical profilometry) and Dr. D. S.-L. Law (ESCA
facility at NCESS) is gratefully acknowledged. The implant
samples were generously provided by the manufacturers. The
authors would like to acknowledge Daresbury NCESS facility
and EPSRC grant ref EP/E025722/1.
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