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With the increasing number of orthodontic treatments using devices containing nickel and
the growing prevalence of nickel allergy in the average population, biocompatibility studies
of these devices have become a topic of major interest. The corrosion behavior of
orthodontic wires is a decisive factor determining their biocompatibility. Therefore four
nickel±titanium guiding arches, a titanium±molybdenum and a stainless steel wire were
analyzed for corrosion behavior under realistic conditions. Pure potentiostatic, pure
mechanical and combined potentiostatic and mechanical stresses were applied to the
specimens. Subsequently, the surfaces of the wires were investigated employing atomic
force microscopy (AFM) and nickel loss was measured with an atomic absorption
spectrophotometer. The results yield information about the relative corrosion tendency of
the wires under in vitro conditions. The wires examined can be classi®ed into two groups,
one with a high and a second group with a low tendency towards corrosion, that is American
Orthodontics Memory wire as well as GAC Neo Sentalloy and Ormco Ni±Ti as well as Unitek
Nitinol respectively. Although corrosion behavior under clinical conditions can not be
directly derived from these results, analyses of wires after clinical usage indicate that
changes of wire surfaces might show the same characteristics under in vitro conditions.
# 1999 Kluwer Academic Publishers
276
Figure 3 Inert macor appliance used for ®xing of the wires in the
Figure 2 Schematic experimental set-up of the electrochemical cell
electrochemical cell.
used.
constructed potentiostate (electronics workshop, AFM and the mean roughness Ra was calculated. In a
Department of Chemical Physics, University of Bonn) third series mechanical stresses were combined with
and a function generator (TG 230, Thurlby-Thandar, potentiostatic polarization for each specimen and again
UK). Additionally a vertically moveable inert glass rod surface characteristics were evaluated.
was integrated for mechanical load application. The set- In the closing part of the study the wires were
up was controlled and data was taken by a personal polarized for 10 min at 0.72 and 1.22 V/NHE in the
computer via an A/D converter board. arti®cial Fusayama saliva, the resulting precipitates were
A de®ned length of 3 cm of each of the specimens was homogenized in an ultrasonic bath and the amount of
exposed as electrode to the electrolyte. Modi®ed dissolved nickel was determined with an atomic
Fusayama arti®cial saliva [20] at 37 C was chosen as absorbtion spectrophotometer (Perkin-Elmer, Norwalk,
the electrolyte as it tends to correlate best in corrosion CT, USA). The linear working range of the spectrometer
experiments with the results obtained from natural saliva selected equates the maximum observed nickel concen-
[21]. The composition of the saliva used is listed in Table tration; thus the measured values of the samples with
II. To determine the rupture potentials, anodic potentio- smallest nickel content have a signi®cantly higher error.
dynamic and potentiostatic polarization were performed
for a ®rst classi®cation of the wires. The specimens were
subjected to a potentiostatic polarization of 0.72 and
2.4. Atomic force microscopy
1.22 mV (NHE) in order to accelerate the natural
The atomic force microscope (AFM) [22] belongs to a
corrosion process which is very slow. Each specimen
new class of non-destructive microscopes for surface
was polarized for 60 s at the above-mentioned values. A
analysis called scanning probe microscopes. The AFM is
reaction between the wire and the electrolyte can be
able to perform surface analysis without direct interac-
observed when the polarization value is higher than the
tion with the specimen's surface. The AFM delivers
rupture potential of the specimen.
three-dimensional realistic impressions of the scanned
In a second experimental series wires were exposed to
surfaces. Scanned areas reach from atomic level up to
mechanical stresses to simulate the intra-oral situation
140 mm square. No extensive preparation of the specimen
during mastication. 10 000 bending cycles were carried
is required, which makes AFM a labor saving, fast
out with a glass rod that moved vertically over a distance
method. From these surface scans of the specimens a
of 1.5 mm with a frequency of 1 Hz. The wires were ®xed
large variety of surface characteristics can be derived and
in the electrolyte with a free wire length of 3 cm by
the average mean surface roughness was chosen to
macor rods with specialized wire clamps (Fig. 3). This is
compare the different wires.
a typical free bending length comparable to the space
The generation of surface scans is performed with a
between two teeth around an extraction site.
very ®ne tip (radius of curvature 20±40 nm) located at the
Subsequently surface scans were taken again with the
end of a cantilever (length and thickness about 200 mm
and 0.5 mm respectively, see Fig. 4). The tip approaches
the specimen's surface and at a distance of approxi-
T A B L E I I Compsition of the arti®cial Fusayama saliva used in this
study mately 100 nm Coulombian forces cause the cantilever to
bend. A laser beam being re¯ected from the back of the
Component (mg 1 ÿ 1) bent cantilever is registered by a segmented photodiode
and each movement of the cantilever causes a shift of the
Sodium chloride 400
Potassium chloride 400 light spot out of the center of the photodiode. This
Calcium chloride-dihydrate 795 information is used to keep the distance between
Sodium hydrogen phosphate-1-hydrate 690 specimen and tip constant by controlling the vertical
Potassium rhodanide 300 position of the probe via piezo-driven positioning
Sodium sul®de 5
devices. Surfaces are scanned in subsequent lines to
Urea 1000
record the whole surface topography. A commercial
277
Figure 4 Sketch of an atomic force microscope.
Figure 5 Surface scans of all wires examined. Top view at
100 6 100 mm. 1 Titanium Memory wire; 2 Neo Sentalloy; 3 Ni±Ti;
4 Nitinol; 5 TMA; 6 Stainless steel.
AFM Nanoscope III from Digital Instruments Inc. (San
Diego, USA) was used. The method is limited to vertical
scanning ranges of about 5 mm. Thus, as several samples After a 1 min potentiostatic polarization at 1.22 V/NHE a
showed massive pitting corrosion after polarization, combination of pitting and area corrosion could be
these wires were measured additionally with an electron observed. Scanning of the surface of the polarized
microscope (JSM T300, Jeol). Titanium Memory with the AFM could only be
performed in smoother areas due to the high vertical
variations caused by corrosion. Thus corrosion processes
were documented additionally with an electron micro-
3. Results
scope (Fig. 7a and b, magni®cation 6 350 and 6 2000,
3.1. Rupture potentials
respectively). The pictures show massive pitting corro-
Table III lists the results of all analyses. The rupture
sion but the true depth of the structures could not be
potential of the titanium±molybdenum wire could not be
determined.
determined. Even polarization over a period of 12 h at a
polarization potential of 2.22 V/NHE did not cause any
material loss. All other products could be classi®ed into a
group with a higher rupture potential (i.e. U > 600 mV/
NHE) and a group with a lower rupture potential (i.e.
U < 600 mV/NHE).
278
(a)
(a)
(b)
Figure 8 (a) Surface scan taken with the AFM from the Nitinol wire in
as-received state. (b) Surface scan (AFM) of a Nitinol wire after a
period of 3 months in the patient's mouth.
(b)
changes in the Ra value could not be ascertained. All
Figure 7 (a) Polarized titanium memory wire. Scan taken with the
electron microscope, magni®cation 6350. (b) Same wire at a
other wires showed no signi®cant nickel loss. Combined
magni®cation of 62000. Destruction of the surface due to pitting mechanical and electrochemical stresses did not have
corrosion is quite obvious. any effect on corrosion behavior, surface structure or
nickel loss compared to pure potentiostatic stress.
Fig. 8a depicts a surface scan of the as-received
Nitinol wire. Scaling is similar to Fig. 6. The unpolarized
sample of Nitinol is much rougher than that of the 4. Discussion
Titanium Memory wire. Nevertheless, surface defects Orthodontic NiTi wires show differences in their
after clinical use are comparable to corrosion processes corrosion behavior. Resultantly the products analyzed
of the Titanium Memory wire due to polarization. This can be split into two categories. Rupture potentials and
can be seen from Fig. 8b, which shows an AFM scan of a nickel loss in combination with changes of the surface
Nitinol wire that remained over a period of 3 months in a roughness were taken into account as indicators of their
patient's mouth. tendency towards corrosion.
Table IV summarizes the surface roughness and nickel The ®rst group is characterized by low rupture
loss determined for all wires. The values are the mean of potentials (i.e. below 600 mV/NHE), has a high tendency
10 measurements, standard deviation is given in towards corrosion and is composed of the Titanium
parentheses. The smoothest wires in as-received state Memory wire and Neo Sentalloy. The Titanium Memory
are the Titanium Memory wire and the stainless steel, all wire showed drastic changes of surface topography after
other products are much rougher. Comparing the surface potentiostatic stress. Pitting and area corrosion were
roughness of the unpolarized wires with the polarized detected with the AFM. Ra values changed signi®cantly.
ones the Ra value only increases signi®cantly for the The changes in surface structure correlated with nickel
Titanium Memory wire. There are no signi®cant changes dissolution in the electrolyte (arti®cial saliva), that was
of the Ra value after polarization for all other wires. more than 100 times greater than the smallest one.
Measured nickel dissolution in the arti®cial saliva was Changes in surface structure were quite small for the Neo
highest for the Titanium Memory wire which correlates Sentalloy but the nickel loss determined was greater by a
very well with the changes of the surface structure by factor of 10±20 in comparison with the other group.
polarization. The second largest nickel loss was The second category is represented by wires with low
determined for Neo Sentalloy, but a correlation with corrosion tendency. The Ni±Ti wire and the Nitinol from
279
T A B L E I V Summary of the results
Titanium Nickel±titanium 110 (25) 180 (60) >290 (180) 23.0 39.4
Memory wire
Neo Nickel±titanium 325 (30) 335 (80) 340 (35) 3.1 17.7
Sentalloy
Ni±Ti Nickel±titanium 335 (100) 260 (65) 215 (25) 0.2 0.2
Nitinol Nickel±titanium 325 (70) 355 (75) 385 (55) 0.1 0.3
TMA Titanium±molybdenum 340 (80) 270 (60) 425 (170) ± ±
Stainless Stainless 80 (35) 65 (10) 55 (10) 0.4 0.7
steel steel
the nickel±titanium products, as well as the TMA and the analyzed wires. The results of the present in vitro study
stainless steel wire from the reference group belong to can not be transferred unrestrictedly to clinical condi-
this category. The rupture potentials of these samples tions. There are many more factors than corrosion that
were higher (i.e. above 600 mV/NHE) and no signi®cant have an in¯uence on biocompatibility. It is important to
changes in surface structure or in the Ra value after discover which surface structures start the corrosion
potentiostatic polarization could be determined. On the process or which structures enhance the corrosion
contrary, a smoothing of the surface was determined for defects. An in situ analysis of corrosion process via
the NiTi wires and stainless steel. This might be AFM and a connected electrochemical cell is planned.
explained by a ¯attening of the peaks and troughs that The results of this experimental set-up could help to
resulted from production. The nickel loss from the wires optimize production processes and to clarify the effects
in this group was much smaller than the one from the of interaction between alloy composition, crystal
wires in the ®rst group. Especially, the TMA wire was structure and surface corrugation on corrosion behavior.
chemically inert. A rupture potential could not be These are not yet totally understood. Another aspect of
detected and due to its composition nickel loss could optimization is the reduction of surface roughness. This
not be expected. will have a positive effect on treatment progress,
Several factors are responsible for varying corrosion aesthetic appearance and plaque retention.
behaviors of the specimen wires. A highly important one
is the alloy composition although the different tendencies
towards corrosion cannot be directly derived from the
alloy composition, which is nearly identical for all NiTi Acknowledgment
wires. However, AFM scanning revealed that each wire The authors wish to thank the Minister fuÈr Wissenschaft
has a typical surface structure resulting from different und Forschung, Nordrhein-Westfalen for ®nancial sup-
production and especially ®nishing processes. The port.
in¯uence of surface corrugation and structural constitu-
tion might be a reason for varying corrosion tendency.
However, the present study is not able to answer the
question as to which one of the stated factors is the most References
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281