archives of civil and mechanical engineering 18 (2018) 941–947

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Original Research Article

Comparative assessment of the corrosion process of

orthodontic archwires made of stainless steel,
titanium–molybdenum and nickel–titanium alloys

Konrad Małkiewicz a,*, Mariola Sztogryn b, Marcin Mikulewicz c,

Andrzej Wielgus d, Janusz Kamiński e, Tadeusz Wierzchoń e
a
Department of Orthodontics, Medical University of Warsaw, Poland
b
Private Practice, Warsaw, Poland
c
Division of Facial Abnormalities, Department of Orthodontics, Medical University of Wroclaw, Poland
d
Wroclaw University Hospital, Wroclaw, Poland
e
Faculty of Materials Science and Engineering, Warsaw University of Technology, Poland

article info abstract

Article history: The phenomenon of corrosion of orthodontic appliances is of interest to both clinicians and
Received 23 November 2017 researchers dealing with the issue of biocompatibility of medical materials. The oral cavity,
Accepted 27 January 2018 due to its temperature fluctuations, changing pH, high humidity, action of mechanical forces
Available online 3 March 2018 and the presence of microorganisms is a favorable environment for degradation of dental
materials. This article presents the comparative assessment of the intensity of corrosion of
Keywords: orthodontic archwires made of alloy steel, nickel–titanium and titanium–molybdenum
Orthodontic wires alloys in laboratory conditions. Corrosion resistance examinations were carried out by
Corrosion means of the impedance and the potentiodynamic methods using an Autolab PGSTAT100
Nickel–titanium potentiostat/galwanostat (Eco Chemie B.V., Holand) with FRA2 module, in non-deaerated
b-Titanium artificial saliva solution at 37 8C. An analysis of the impendence method's data showing that
Stainless steel the highest corrosion resistance is observed for NiTi arches (3M, USA), while the lowest
resistance for SS arches (3M, USA). These observations were confirmed by the data obtained
from potentiodynamic tests; it was observed that the average corrosion current density [Icor]
was the lowest for nickel–titanium archwires (3M, USA) and averaged 2.50
103 mA/cm2.
The highest Icor corrosion current was observed in the case of steel wires from the same
manufacturer and averaged 4.96
102 mA/cm2.
© 2018 Politechnika Wrocławska. Published by Elsevier B.V. All rights reserved.

* Corresponding author at: Department of Orthodontics, Medical University of Warsaw, ul. Nowogrodzka 59, 00-246 Warsaw, Poland.
E-mail address: konrad.malkiewicz@interia.pl (K. Małkiewicz).
https://doi.org/10.1016/j.acme.2018.01.017
1644-9665/© 2018 Politechnika Wrocławska. Published by Elsevier B.V. All rights reserved.
942 archives of civil and mechanical engineering 18 (2018) 941–947
1. Introduction
The use of fixed appliances for the treatment of malocclusion
is a common therapeutic method in modern orthodontics.
The basic elements that make up thin-arch fixed appli-
ances are brackets attached to the teeth, rings embracing
molar teeth and arches connecting the individual parts of the
appliance.
Orthodontic brackets can be made of ceramics, composite
materials or metal alloys. The commonly used metal brackets
are produced with the use of iron alloys with chromium,
cobalt, nickel and manganese [1–3]. For the sake of better
biocompatibility, manufacturers also provide brackets with
lower content of nickel or products made from titanium
alloys.
Orthodontic archwires, which are extremely diverse as far
as material is concerned, are elements generating forces that
allow movement of teeth as well as provide the base along
which they move, for example when the so-called slip
mechanics is applied.
The main material used in production of orthodontic
archwires is austenitic alloy steel grade X5CrNi18-10
(ASTM304) containing about 18% chromium and 8% nickel [4].
Archwires are also made from cobalt-chromium-nickel
alloy (CoCrNi), containing about 40% of cobalt, 20% of
chromium, 15% of nickel, 16% of iron, and an addition of
molybdenum and manganese [4].
In the 1980s orthodontic archwires made of titanium–
molybdenum alloys/TMA, also called b-titanium, were intro-
duced. They were composed mainly of titanium, constituting
about 70% of their mass, and molybdenum – about 11% of the
weight of the product [4,5].
Nickel–titanium archwires, which are becoming more and
more common in orthodontic practice, contain about 55% of
nickel and 45% of titanium [6]. Their variants are enriched with
copper and chromium additions, and often their composition
is a manufacturer's secret, due to unique mechanical proper-
ties of modified wires, so desirable in the process of
orthodontic treatment.
Orthodontic brackets remain in the oral cavity for the whole
period of treatment, which is about two years. Metal alloy
based archwires are components of fixed appliances for a
period of one to several months, depending on therapeutic
needs. The same is true for steel or polyurethane ligatures
used to fix archwires to brackets.
During that time metal alloys are exposed to constant
humidity, variable temperatures and pH fluctuations. Saliva,
in which metal elements are immersed, is an electrolyte, and
the material variety of the used elements makes the
orthodontic appliance a kind of a cell in the oral cavity
environment, being subjected to continuous electrochemical
processes.
The phenomenon of corrosion of fixed orthodontic braces is
of interest to both clinicians and researchers dealing with the
issue of biocompatibility of medical materials. The oral cavity,
due to its temperature fluctuations, changing pH, high
humidity, action of mechanical forces and the presence of
microorganisms [7,8], is a favorable environment for degrada-
tion of dental materials. It should also be mentioned that
individual elements forming the orthodontic appliance are not
made of the same type of alloy, but of materials of different
electrochemical reactivity that could potentially create a
corrosion center [9–11]. The degradation process may be
intensified by presence of bacterial plaque [7], whose effective
removal may be hampered when the appliance's parts adhere
to the surface of teeth.
Destruction of dental materials in the oral cavity is often
macroscopically unnoticeable. Small centers of degradation
appear on their surface, and, with time, such centers join
together. Constant changes in physical and chemical param-
eters in the oral cavity support and intensify the course of
certain processes. These processes lead to very serious
weakening of the structure of restorative reconstructions,
prostheses, orthodontic archwires and brackets as well as
other elements of fixed appliances. As a result of corrosion,
dental materials based on metal alloys undergo gradual
degradation, not only losing their mechanical characteristics
or visual qualities, but also releasing potentially harmful metal
ions into the external environment [10–12]. These include first
of all nickel, cobalt or chromium, which are generally
recognized as biologically harmful [12,13].
Although it is assumed that the amount of metal ions
released from dental materials into the oral environment is
not sufficient to produce acute symptoms of intoxication, their
extended supply can cause both localized and systemic
adverse effects. Corrosion affecting dental materials may
result in unesthetic discoloration around amalgam fillings or
orthodontic brackets, whereas metal ions released into the
external environment may increase or induce the formation of
pre-malignant lesions in the structure of oral mucosa [14]. In
the mechanism typical for type IV allergic reactions, nickel
ions released from archwires of orthodontic appliances may
cause ulceration of the lips, mucous membrane or tongue,
localized swelling or taste disorders [15,16].
In the light of the above, it seems very important to
continuously monitor the biological characteristics of com-
mercially available medical materials in the context of the
safety of their use.
The aim of the study was a comparative in vitro assessment
of corrosion susceptibility of six different types of orthodontic
archwires (made of alloy steel, nickel–titanium and titanium–
molybdenum alloys) in artificial saliva solution with the use of
both impedance and potentiodynamic methods.
2. Material and methods
The study material were orthodontic archwires with a cross-
section of 0.017 by 0.025 in. (0.04
0.06 cm) from two different
manufacturers: 3M (USA) and Rocky Mountain Orthodontic
[RMO] (USA), made of alloy steel /ASTM304-labeled SS/, beta-
titanium alloys /b-TMA/ and nickel–titanium alloys /NiTi/.
From the orthodontic archwires mentioned above, six
specimens of 2 cm length were prepared, five for each type of
arch. The surface of the tested materials was 0.4 cm2.
Electrochemical tests were performed in artificial saliva
[17], whose composition is shown in Table 1.
Corrosion resistance examinations were carried out by
means of the impedance and the potentiodynamic methods
 archives of civil and mechanical engineering 18 (2018) 941–947 943

Table 1 – Chemical composition of artificial saliva solution.

Compound NaCl KCl NaH2PO4 CO(NH2)2 CaCl22H2O Na2S9H2O
3
Amount (g/dm ) 0.4 0.4 0.780 1 0.795 0.005

using an Autolab PGSTAT100 potentiostat/galwanostat (Eco
Chemie B.V., Holand) with FRA2 module, in non-deaerated
Ringer's solution at 37 8C. Prior to electrochemical studies, the
samples were exposed to a corrosive solution in current-free
conditions for 120 min. Impedance examination were con-
ducted in a three-electrode setup: the test electrode – reference
electrode (saturated calomel electrode (SCE)) – auxiliary
electrode (platinum), with the frequency ranging from
105 Hz to 103 Hz and the using AC signal with an amplitude
of 5 mV. Corrosion cell was kept in a Faraday cage. EIS methods
were recorded in the potentiostatic mode at open circuit
potential (EOCP). Eco Chemie Analyst software [EQUIVRT –
Baukamp program] was used for processing and fitting the
impedance spectra. Equivalent circuit (EC) with two time
constants R(RQ)(RQ) (Fig. 1) was used. Obtained spectra were
presented in the form of Bode and Nyquist plot.
Potentiodynamic test were conducted in an identical tri-
electrode setup, up to a potential of 3000 mV, or up to
achieving currents over 10 mA/cm2. The test material was
polarized with a potential sweep rate of 0.2 mV/s.
Statistical analysis was performed with STATISTICA 8.0
software. In the testing of statistical hypotheses the signifi-
cance level of a = 0.05 was assumed.
For each continuous variable, basic statistics were calcu-
lated: number (n), arithmetic mean ðxÅÞ, standard deviation (s),
median, minimum and maximum values, as well as skewness
and kurtosis indices. NIR test, among others, was used as post
hoc test. Student's t-test was used for analysis of dependent
variables.
3. Results
Fig. 2 shows Nyquist plots for the studied archwires. The
determined resistances and dependence between various
metallic materials are similar to data obtained in potentiody-
namic tests (Fig. 4).
The highest resistance was observed in the case of
orthodontic archwires made of NiTi alloy, while the lowest
resistance was noted for archwires made of alloy steel type
ASTM304 (Table 2).
An analysis of Bode plots shown in Fig. 3 indicates the
presence of two time constants proving at least two
electrochemical processes occurring on the studied materials.
Electrochemical parameters of the capacitive peak occurring
in the high frequency range (in all analyzed cases) indicate the
diffusion (n = 0.55  0.05) character of the analyzed layer. The
obtained result is undoubtedly due to the roughness of the
orthodontic archwires examined in the study. For the
dominant capacitive peaks, the values of ‘‘n’’ of about 0.9
indicate the capacitive nature of the layer, which undoubtedly
translates into the minimum current densities observed in
potentiodynamic tests (Table 3). The observed differences in
the value of parameter ‘‘n’’ between materials (nNiTi = 0.95,

Fig. 1 – Electric equivalent circuit (EC) with two time constant model R(RQ)(RQ) used for interpretation of the corrosion behavior
of NiTi alloy in artificial saliva solution.
Re – solution, Rp – resistance of dielectric layer; Rt – charge transfer resistance through double layer; CPE1 – capacitance of
constant phase element of passive layer, CPE2 – capacitance of constant phase element of double layer.

Fig. 2 – Nyquist plots for materials exposed to artificial saliva solution at 37 8C; continuous line (match), dashed line (data).
944 archives of civil and mechanical engineering 18 (2018) 941–947

Table 2 – Exemplary electrochemical values of examined orthodontic wires (impedance tests).

Dielectric layer Electric double layer

3M RMO 3M RMO
2
NiTi R[V cm ] 5.20E+02 7.21E+02 1.50E+07 8.07E+06
Y0OCP[F/cm2*sn1] 1.08E04 2.06E04 1.47E05 1.63E05
n 0.65 0.59 0.96 0.95
B-TMA R[Vcm2] 5.32E+02 7.27E+02 6.08E+06 6.14E+06
Y0OCP[F/cm2*sn1] 4.21E04 5.31E04 3.61E05 3.72E05
n 0.55 0.51 0.92 0.94
SS/ASTM304/ R[Vcm2] 1.61E+02 3.92E+02 2.58E+06 3.64E+06
Y0OCP[F/cm2*sn1] 6.41E04 2.55E04 3.26E05 3.14E05
n 0.55 0.6 0.88 0.9

Fig. 3 – Bode plots of the examined orthodontic wires made by (A) 3M and (B) RMO. Continuous line (match), dashed line (data).

Table 3 – Chemical composition of TMA wires in EDS of ions through the electric double layer (resistance Rt)
examinations in defected and non-defected areas (% (Table 2) of 3.6
106 V cm2 (RMO) and 2.6
106 V cm2 (3M)
weight). respectively, the decrease of the value of parameter ‘‘n’’ down
to 0.90 and 0.88 respectively, without doubt contributes to the
Ti-K Zr-L Mo-L Sn-L
reduction of pitting corrosion resistance of 3M wires observed
Defected area 76.95 4.92 11.12 4.65 during potentiodynamic tests. This is demonstrated by the
Non-defected area 77.95 4.60 10.70 4.50
breakthrough potential (Enp) of 1200 mV for RMO wires and
only 480 mV for 3M wires (Fig. 4).
Fig. 4 illustrates potential potentiodynamic curves of the
nTMA = 0.92, nSS = 0.88–0.90), translate into differences in examined orthodontic wires. Their analysis confirmed differ-
durability of passive layers. This dependence is strongly ent durability of the passive layers formed spontaneously on
marked in the case of steel orthodontic archwires. Despite the tested materials exposed to artificial saliva solution at
obtaining comparable values of the resistance of the passage 37 8C. In the case of titanium alloy (b-TMA), irrespective of the

Fig. 4 – Potentiodynamic curves of tested materials (NiTi, SS, TMA) depending on manufacturer (A) 3M; (B) RMO.
 archives of civil and mechanical engineering 18 (2018) 941–947 945

Fig. 5 – Corrosion damage of tested materials after potentiodynamic tests in artificial saliva solution exposed at 37 8C.

manufacturer, the passive layer is durable and does not
corrode throughout the range of tested potentials (up to
3000 mV). The minimum increase of current density (at about
1800 mV) is probably due to a change in the polymorphic form
of titanium oxide (TiO2). In the range of high potentials, soluble
molybdenum oxides are also formed. This is evidenced by
corrosion damage of the layers (Fig. 5), slight depletion of
molybdenum from the exposed area (EDS) (Table 3) as well as
by the Pourbaix diagram for molybdenum (Mo), indicating the
possibility of formation of soluble oxides.
In the case of NiTi alloy, the durability of the layer is high,
limited only by the process of oxygen release from the solution
(at about 1300 mV) occurring on the surface of the nickel
phase. At the same time, degradation of the base in the form of
few minimal pits is observed (in the range of high potentials).
In the case of alloy steel, the shape of the curves indicates
sensitivity of the base to pitting corrosion, whose intensity
varies with the technology of manufacture of orthodontic
wires used by the two producers being discussed. Comparable
chemical compositions of the studied alloys ensure similar
corrosion resistance, while a significant reduction of the
passive area (3M alloy) is due to a non-fully conducted
normalization process applied after the stretching process.
This is evidenced by the location of corrosion damage in the
central zone of orthodontic wires (Fig. 5).
An analysis of the data included in Table 4 confirmed the
results of impedance tests, showing that the highest resis-
tance is observed for NiTi arches (3M), while the lowest
resistance for SS arches (3M). In the case of data obtained from
potentiodynamic tests, it was observed that the average
corrosion current density [Icor] was the lowest for nickel–
titanium archwires from 3M (USA) and averaged
2.50
103 mA/cm2. The highest Icor corrosion current was
observed in the case of steel wires from the same manufac-
turer and averaged 4.96
102 mA/cm2.
The mean values of the Icor corrosion current together with
the values of the basic measurements' statistics for the six
groups of evaluated materials are shown in Table 4.
A statistical analysis at significance level a = 0.05 showed
that the average corrosion current measured for orthodontic
archwires made of stainless steel alloys was significantly
higher than the corrosion current measured for wires made of
titanium–molybdenum and nickel–titanium alloys. The pre-
sented results of statistical evaluation indicate that steel
arches are significantly more susceptible to corrosion than
arches made of the other materials assessed in the study.
At the same time it was observed that the mean value of Icor
was significantly higher for 3M steel archwires compared to
the mean value measured for steel archwires from RMO.
The results of the above statistical analysis are presented in
Table 5.
During the next stage of analysis of obtained data, the
average corrosion currents Icor measured for titanium–molyb-
denum and nickel titanium archwires were compared. The

Table 4 – Mean values of corrosion current density (Icor) for the evaluated materials.
Group No. Producer Arch No. of Icor (mA/cm2) Median Minimum Maximum Standard
material samples deviation
1 3M NiTi 5 2.54E03 2.32E03 1.95E03 3.54E03 0.60E03
2 3M SS 5 49.6E03 58.0E03 13.6E03 94.5E03 32.0E03
3 3M TMA 5 6.52E03 5.90E03 4.40E03 10.1E03 2.13E03
4 RMO NiTi 5 3.90E03 3.16E03 3.03E03 5.94E03 1.25E03
5 RMO SS 5 26.7E03 26.6E03 24.9E03 29.3E03 1.76E03
6 RMO TMA 4 4.68E03 4.69E03 3.26E03 6.08E03 1.27E03
946 archives of civil and mechanical engineering 18 (2018) 941–947

Table 5 – Comparison of mean values of corrosion current Ikor in relation to the assessed material groups (NIR test).
Producer Arch material Group No. Icor [mA/cm2] X1000 1 2 3
3M NiTi 1 2.537 ****
RMO NiTi 4 3.898 ****
RMO TMA 6 4.678 ****
3M TMA 3 6.520 ****
RMO SS 5 26.740 ****
3M SS 2 49.620 ****
Numerical values for which ‘‘****’’ designations are in the same column or in the same row in the table do not differ significantly from each
other at the level of a = 0.05.

Table 6 – Comparison of mean values of corrosion current Icor measured for titanium–molybdenum and nickel–titanium
archwires.
Producer Arch material Group No. Icor [mA/cm2]
1000 1 2 3
3M NiTi 1 2.537 ****
RMO NiTi 4 3.898 **** ****
RMO TMA 6 4.678 **** ****
3M TMA 3 6.520 ****
Numerical values for which ‘‘****’’ designations are in the same column or in the same row in the table do not differ significantly from each
other at the level of a = 0.05.

assessment of the values indicated that at the assumed level of
significance a = 0.05, archwires made of TMA alloys corrode
significantly faster than wires made of nickel–titanium alloys.
At the same time, no significant differences were observed in
the dynamics of the corrosion process for orthodontic
archwires made from the same material groups depending
on their manufacturer.
The results of the above statistical evaluation are presented
in Table 6.
4. Discussion
Over the past few decades we have observed significant
progress in development of materials and products used in
orthodontic treatment. As mentioned above, most compo-
nents of orthodontic fixed appliances are made of metal alloys
that are susceptible to corrosion in the oral cavity environ-
ment. This implies changes in their mechanical and optical
properties, it also conditions release of cytotoxic and genotoxic
metal ions into the oral environment. The conducted research
shows that the highest resistance to corrosion is demonstrated
by archwires made of nickel–titanium alloys, whereas the
lowest resistance is characteristic for archwires made of alloy
steel /ASTM304/. At the same time, the analysis of the results
indicated that susceptibility to corrosion of nickel–titanium
and titanium–molybdenum wires was significantly lower than
that of steel wires, regardless of the manufacturer of the
materials.
Available literature includes publications describing exam-
ination of resistance to corrosion of orthodontic archwires,
using the same methods (EIS and LSV). Their results are
equivocal.
Suarez et al. [18] evaluated the corrosion potential of lingual
archwires from Ormco (USA). The authors assessed the
sequence of wires of different diameters and cross-sections
used for the treatment of malocclusion with the lingual
technique. An analysis of the results showed that the steel
wires evaluated in this study demonstrated significantly higher
corrosion potential than NiTi, CuNiTi and TMA archwires.
In the study by Paskhir et al. [19], the authors compared the
corrosion potential of steel archwires from G&H Wire
Company (India) and nickel–titanium wires made by Ortch-
otechnology (USA), stored in Ringer's solution. The analysis of
the results showed no significant differences between the
evaluated orthodontic wires as far as the Icor value.
Barcelos et al. [20] studied susceptibility to corrosion of
orthodontic archwires from Morelli Ortodontia (Brazil). The
authors compared the potential and corrosion current during
incubation of orthodontic wires in artificial saliva solution at
pH 3 and 5, observing that the steel archwires assessed in the
study demonstrated higher resistance to corrosion than the
nickel–titanium ones.
It is possible that the observations, which were in contrast
to the previously described publications, were influenced by
extremely low pH in the environment of the study, which is
not found in oral conditions except when consuming acidic
foods or beverages.
In the study by Pun and Berzins [21], the authors assessed
electrochemical parameters describing the phenomenon of
corrosion of orthodontic wires placed in solutions of artificial
saliva at different temperatures. They examined nickel–
titanium and nickel–titanium–copper wires from Ormco
(USA) and nickel–titanium wires made by 3M (USA). At 37 8C
the corrosion potential assumed the highest values for 3M's
nickel–titanium archwires and the lowest values for Ormco's
nickel–titanium–copper wires. At this point it should be noted
that this relationship varied with thermal conditions, which
may indicate different dynamics of corrosion processes
affecting orthodontic materials when consuming cold or
warm foods and drinks. However, since extreme temperature
fluctuations in the oral cavity tend to be short, measurements
taken at 37 8C should be considered as being closest to clinical
conditions.
 archives of civil and mechanical engineering 18 (2018) 941–947
Briceno et al. [22] evaluated the corrosion potential of
nickel–titanium orthodontic wires from different manufac-
turers. Despite similar percentage composition of used alloys,
the authors observed large differences between Icor values for
individual wires ranging from 3.00 to 0.22 mA/cm2 (log)
depending on the product.
The results of studies and data from literature clearly show
the occurrence of corrosion of orthodontic archwires in
laboratory conditions. Due to methodological differences, it
is not possible to compare them directly, however they do
indicate that archwires containing titanium are more resistant
to corrosion than orthodontic wires made of stainless steel.
This phenomenon can be explained by formation of a layer of
titanium oxide on their surface, protecting the material
against the influence of external factors [23], more than
Cr2O3 oxides formed in the case of steel wires. Unfortunately,
the results of the current study confirm that none of the
evaluated orthodontic archwires is biologically inert and
constitutes a potential source of metal ions released into
the oral cavity environment during orthodontic treatment.
In the light of these observations, it is advisable to monitor
the biocompatibility of medical products and to use in clinical
conditions only those materials that can secure the widest
margin of safety for the patient, as well as to use surface
engineering methods in order to increase their resistance to
corrosion [24].
5. Conclusions
1. The studied orthodontic archwires made of alloy steel
/ASTM304/, beta-titanium alloy /b-TMA/ and nickel–titani-
um alloy /NiTi/ corroded in the environment of artificial
saliva.
2. The highest resistance to corrosion was observed in NiTi
alloy archwires, while the lowest corrosion resistance was
noted in the case of steel wires.
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