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REVIEW
Blackwell Science, Ltd
S. A. Thompson
Department of Adult Dental Health, University of Wales College of Medicine, Cardiff, UK
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previous shape, by forming strong, directional and thus lowering the total number of bonding electrons.
energetic electron bonds to pull back displaced atoms to However, formation of a detrimental second phase
their previous positions; the effect of this transforma- NiTi3 occurs if excess nickel is added in attempts to
tion is instantaneous. lower the TTR.
It is possible using the shape memory effect to educate
or place the NiTi alloy into a given configuration at a
Stress-induced martensitic transformation
given temperature. This can be carried out at lower
temperatures which deform the NiTi with a very low The transition from the austensitic to martensitic phase
force and results in the ‘twins’ all occurring in the can also occur as a result of the application of stress,
same direction. When the NiTi is heated through its such as occurs during root canal preparation. In most
transformation temperature it will recover its original metals, when an external force exceeds a given amount
‘permanent’ shape (Fig. 2). The application of shape mechanical slip is induced within the lattice causing
memory to orthodontics is discussed later. In terms of permanent deformation; however, with NiTi alloys a
endodontology, this phenomenon may translate to the stress-induced martensitic transformation occurs, rather
ability to remove any deformation within nickel– than slip. This causes:
titanium instruments by heating them above 125 °C • a volumetric change associated with the transition
(Serene et al. 1995). from one phase to the other and an orientation
The transition temperature range for each nominal relation is developed between the phases
55-Nitinol alloy depends upon its composition, as this • the rate of the increase in stress to level off due to
causes considerable variability in the number of electrons progressive deformation (Fig. 5) even if strain is
available for bonding to occur and is constant for a par- added due to the martensitic transformation. This
ticular NiTi alloy composition. The TTR of a 1 : 1 ratio results in the so-called super-elasticity (Fig. 4), a
of nickel and titanium is in the range of –50 to +100 °C. movement which is similar to slip deformation. The
Reduction in the TTR can be achieved in several ways; differences between the tensile behaviours of NiTi
in the manufacturing process both cold working and and stainless steel alloy can be seen in Fig. 6.
thermal treatment can significantly affect TTR, as • springback when the stress decreases or stops
can altering the nickel : titanium ratio in favour of without permanent deformation occurring (Fig. 3).
excess nickel or by substituting cobalt for nickel, atom Springback is defined as load per change in deflec-
for atom. Cobalt substitution produces alloys with tion (Andreasen & Morrow 1978), to the previous
the composition NiTixCo1-x. The TTR can be lowered shape with a return to the austenite phase, pro-
progressively by continued substitution of cobalt for vided the temperature is within a specific range
nickel as cobalt possesses one less electron than nickel, (Fig. 4).
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The plastic deformation that occurs in NiTi alloys range (SRTR). This has also been termed ‘mechanical
within or below the TTR is recoverable, within certain memory’ (Buehler & Wang 1968). This is unlike conven-
limits, on reverse transformation. It is this phenome- tional metallic stress-strain behaviour where elastic
non of crystalline change which gives rise to the response in conventional alloys is recoverable, but is
shape memory effect of the material and the super- small in size; and where larger strains are associated
elastic behaviour. The part of the RTTR in which ‘shape with plastic deformation, that is not recoverable
recovery’ occurs is termed the shape recovery temperature (Fig. 7).
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The super-elasticity of nickel–titanium allows deforma- metals which can occur in all possible combinations. As
tions of as much as 8% strain to be fully recoverable such, a second group of Nitinol alloys can be formed if
(Fig. 8), in comparison with a maximum of less than the NiTi alloy contains more nickel and as this approaches
1% with other alloys, such as stainless steel. Although 60% (wt) Ni an alloy known as 60-Nitinol forms. The
other alloys such as copper–zinc, copper–aluminium, shape memory effect of this alloy is lower, although
gold– cadmium and nickel–niobium have been found to its ability to be heat-treated increases. Both 55 and 60-
have super-elastic properties (Buehler & Wang 1968), Nitinols are more resilient, tougher and have a lower
nickel–titanium is the most biocompatible material and modulus of elasticity than other alloys such as stainless
has excellent resistance to corrosion. steel, Ni–Cr or Co–Cr (Fig. 8). Table 1 shows the values
An alloy system is an aggregate of two or more for typical properties of Nitinol alloys.
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Physical
Density (gm cm3) 6.45
Melting point (°C) 1310
Magnetic permeability <1.002
Coefficient of thermal expansion (× 106/°C) 11.0 6.6
Electrical resistivity (ohm-cm) 100 × 10 −6 80 × 10 −6
Hardness 950 °C (Furnace cooled) 89 RB
Hardness 950 °C (Quenched-R.T. water) 89 RB
Mechanical
Young’s modulus (Gpa) 120 50
Yield strength (Mpa) 379 138
Ultimate tensile strength (Mpa) 690–1380
Elongation 13–40%
Shape memory
Transformation temperature (°C) –50 to +100
Latent heat of transformation 10.4 BTU lb–1
Shape memory recoverable strain 6.5–8.5%
Super-elastic recoverable strain up to 8%
Transformation fatigue life several hundred
at 6% strain cycles
at 2% strain 105cycles
at 0.5% strain 107cycles
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flexibility, (Fig. 8) thereby decreasing canal transportation, ductivity and the mass of the material. The corrosion
and to allow high resistance to fatigue. resistance of Nitinol alloys was evaluated by Buehler
Once the alloy has been manufactured, it undergoes & Wang (1968) who reported that they performed
various processes before the finished wire can be machined adequately in a marine environment.
into a root canal instrument (Fig. 11). Essentially, the Duerig (1990) described applications for shape memory
casting is forged in a press into a cylindrical shape prior NiTi alloys grouped according to the primary function of
to rotary swaging under pressure, to create a drawn the memory element. An example of (i) free recovery was
wire. The wire is then rolled to form a tapered shape with NiTi eyeglass frames, (ii) constrained recovery was couplings
even pressure from a series of rollers applied to the wire. for joining aircraft hydraulic tubing and electrical con-
During the construction phase, other processes are carried nectors, (iii) work production was actuators both electrical
out on the rod-rolled wire including drawing the wire and thermal and (iv) super-elasticity was orthodontic
onto a cone, annealing the wire in its coiled state, descal- archwire, guidewires and suture anchors.
ing and further fine wire drawing followed by repeated Further uses of the super-elastic properties of NiTi
annealing with the wire in a straight configuration. This wire were described by Stoeckel & Yu (1991). As super-
stage is followed by drawing the actual profile or cross- elasticity is an isothermal event, applications with a well
sectional shape of the wire, e.g. imparting either a round, controlled temperature environment are most successful, e.g.
square or oblong shape prior to a cleaning and conditioning in the human body. NiTi wire has been used as ortho-
process. The finished wire is stored on reels prior to dontic archwire and springs, in Mammalok® needle wire
machining. This process is illustrated in Fig. 11. localizers (to locate and mark breast tumours), guidewires
for catheters, suture needles and anchors, the temples and
bridges for eyeglasses, and, in Japan, underwire brassieres.
Uses of nickel–titanium alloy
Nitinol wire was first used in the self-erectile action of a
Use of nickel–titanium alloys in dentistry
disc on rod antenna that recovered its prefolded shape
above the transition temperature of the alloy (Buehler &
Orthodontics
Wang 1968). The unique ‘mechanical memory’ of 55-
Nitinol allowed it to recover its original shape after Initially NiTi alloys were used in the construction of
mechanical distortion by heating it above the transition orthodonic archwires. Extensive research published
temperature. The rate of recovery of the antenna was in the materials science and orthodontic journals has
determined by the rate at which the critical temperature allowed the properties of the material to be appreciated
was reached, which depended on the thermal con- and used in an appropriate clinical manner. Many of
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these studies have relevance to an understanding of work-hardening process, thus affecting the properties of
NiTi alloys used in endodontology and a brief descrip- shape memory or super-elasticity.
tion of this literature is described. Kusy & Stush (1987) observed a discrepancy between
NiTi wires were first used in orthodontics by Andreasen the stated dimensions of wires of 10 Nitinol and seven beta
& Hilleman (1971), who observed differences in the titanium wires; the sizes were smaller 95% of the time
physical properties of Nitinol and stainless steel and neither wire obeyed simple yield strength relationships.
orthodontic wires that allowed lighter forces to be used. The ultimate tensile strength of Nitinol wires increased
The strength and resilience of NiTi wires meant there with decreasing cross-sectional area and also appeared
was a reduction in the number of arch wire changes more ductile with increasing cross-sectional area.
necessary to complete treatment. Rotations of teeth could Yoneyama et al. (1992) assessed the super-elasticity
be accomplished in a shorter time, without increasing and thermal behaviour of 20 commercial NiTi ortho-
patient discomfort. Nitinol wires showed better resistance dontic arch wires. A three-point bending test allowed
to corrosion so were felt more appropriate for intraoral load-deflection curves to be determined and differential
use than stainless steel. scanning calorimetry was used to determine thermal
Andreasen & Morrow (1978) observed the unique behaviour due to phase transformation of the alloy.
properties of Nitinol, including its outstanding elasticity Substantial differences were noted between the wires;
(which allows it to be drawn into high-strength wires) some showed super-elasticity (which occurs with the
and its ‘shape memory’ (which allows the wire when stress induced martensitic transformation), whilst other
deformed, to ‘remember’ its shape and return to its original wires only had good springback qualities. Super-elasticity
configuration). The most important benefits of Nitinol was only exhibited by wires showing high endothermic
wire were its construction as a resilient, rectangular energy in the reverse transformation from the martensitic
wire that allowed simultaneous rotation, levelling, tipping phase to the parent phase and with low load/deflection
and torquing movements, to be accomplished early in ratios. These wires showed nearly constant forces in
treatment. Limitations to the use of the material were the unloading process, a desirable physiological property
noted, such as the time taken to bend the wires, the for orthodontic tooth movement; the lower the L/D ratio,
necessity of not using sharp-cornered instruments that the less changeable is the force which the wire can display.
could lead to breakage and the inability to be soldered or Clearly, there are differences in the mechanical
welded to itself. Overall, the authors felt the material properties and thermal behaviour of NiTi alloy which
represented a significant improvement over conventional vary with composition, machining characteristics and
arch wire and was a valuable addition to the orthodontist’s differences in heat treatment during manufacture. The
armamentarium. need for correct production of NiTi alloys was stressed
Burstone & Goldberg (1980) observed beneficial by Yoneyama et al. (1992) in order that the desired
characteristics such as low modulus of elasticity clinical characteristics could be obtained.
combined with a high tensile strength that allowed Evans & Durning (1996) reported the differences in
wires to sustain large elastic deflections due to the very formulations of nickel–titanium alloy and their applica-
high springback quality. Limitations such as restricted tions in archwire technology. A review article published
formability and the decrease of springback after bending by Kusy (1997) described the properties and characteristics
prompted investigations into other alloys, such as beta of contemporary archwires from initial development
titanium. Drake et al. (1982) concluded that Nitinol to their current use in variable modulus orthodontics
wire was suitable mainly for pretorqued, preanglulated as advocated by Burstone (1981). The variation in
brackets. composition of nickel–titanium alloys was discussed
Miura et al. (1986) tested a new Japanese NiTi alloy together with the influence this had on the properties
and compared it to stainless steel, Co–Cr–Ni and Nitinol of the resultant alloy.
wires. Japanese NiTi alloy exhibited super-elastic properties
and was least likely to undergo permanent deformation
Corrosion behaviour of NiTi orthodontic wires
during activation. The Nitinol wire showed less per-
manent deformation and excellent springback qualities in The corrosion behaviour of Nitinol orthodontic wires
comparison with the stainless steel and Co – Cr–Ni wires, was compared with stainless steel, cobalt-chrome and
however, load and deflection were almost proportional, β-titanium by Sarkar et al. (1979). The wires were
indicating lack of super-elastic qualities. This may have exposed to a 1% NaCl solution via an electrochemical
been due to the fact that Nitinol was manufactured by a cyclic polarization technique. Scanning electron
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microscopy and energy dispersive X-ray analysis was occurred on electrolytically corroded Nitinol wires, with
used to determine differences between pre- and postpo- loosely bound corrosion products; however, after clinical
larized surfaces. The Nitinol alloy was the only specimen use, no differences in surface characteristics were obvious
to exhibit a pitting type corrosion attack, which the when comparing pre- and postoperative SEM photographs.
authors concluded warranted further investigation. There was no significant difference between the surface
Sarkar & Schwaninger (1980) studied the in vivo oxygen content of Nitinol compared to stainless steel, which
corrosion characteristics of seven Nitinol wires in clinical would suggest that there were no differences in the clinical
use for 3 weeks to 5 months. Scanning electron micros- performance of the two wires, in terms of corrosion.
copy revealed the presence of numerous, round-bottomed,
corrosion pits interspersed with corrosion products rich
Effects of sterilization on NiTi orthodontic wires
in titanium. This was presumed to be a mixed oxide of
titanium and nickel. Fractured surfaces of Nitinol wires Mayhew & Kusy (1988) examined the effects of dry
showed small equiaxed dimples that resulted from heat, formaldehyde-alcohol vapour and steam autoclave
microvoid coalescence within the grain-boundary zones. sterilization on the mechanical properties and surface
There appears to be correlation with in vitro (Sarkar topography of two different nickel–titanium arch wires.
et al. 1979) and in vivo corrosion of Nitinol. The wires were being reused clinically, due to their high
The performance of wires used in orthodontics can be cost. After sterilization, the elastic modulus and tensile
affected by corrosion in the mouth. Edie & Andreasen properties were determined for Nitinol and Titanal wires
(1980) examined Nitinol wires under SEM as received (Lancer Pacific, Carlsbad, CA, USA); laser scanning
from the manufacturer and following 1 month to was employed to detect surface alterations caused by
1 year’s use in the mouth. They found no corrosion tarnish, corrosion or pitting.
of the Nitinol wires with maintenance of a smooth, No detrimental effects were noted, and the nickel–
undulating surface. In contrast, stainless steel wires titanium arch wires maintained their elastic properties,
showed sharp elevations of metal particles on their surface. had excellent resilience and low load-deflection rates,
Clinard et al. (1981) used polarization resistance and which led the authors to conclude that stabilized
zero resistance ammetry to study the corrosion beha- martensitic alloys such as Nitinol could be heat sterilized,
viour of stainless steel, cobalt– chromium, beta-titanium without forming tempered martensite. The specular
and Nitinol orthodontic springs. They also studied the reflectivity for Nitinol was determined by laser spectros-
effect of coupling the wires to stainless steel brackets. copy and ranged from 1.1 to 4.6 µ W. Sterilization did
In orthodontic treatment, the corrosion behaviour of not appear to effect surface topography adversely.
the wires was affected by coupling to the brackets. The load-deflection characteristics of NiTi wires after
The effects of beta-titanium and cobalt–chromium were clinical recycling and dry heat sterilization were examined
comparable showing less corrosion than the other by Kapila et al. (1992). Thirty 0.016 inch work-hardened
wires, however, Nitinol was shown to be inferior to Nitinol and austensitic NiTi wires were subjected to a
stainless steel, with a tendency to pitting attack. The three-point bending test in an ‘as received’ condition,
authors concluded that over the relatively short period and after one and two cycles of dry heat sterilization for
of orthodontic treatment, the effect of the corrosion did 5 min at temperatures that ranged from 203 to 217 °C.
not appear to be deleterious to the mechanical pro- It was observed that recycling these wires after sterili-
perties of the wires, and should not significantly effect zation causes significant changes to the loading and
the outcome of treatment. unloading forces associated with the wires, together with
To assess corrosion potential, Edie et al. (1981) com- a reduction in the pseudo-elasticity of NiTi wires and an
pared Nitinol wire with stainless steel wire in clinical increase in the stiffness of both the Nitinol and NiTi wires.
use for periods ranging from 1 to 8 months. Scanning Three types of nickel–titanium wires, a β-titanium
electron microscopy was used to assess surface charac- and a stainless steel wire were sterilized by either cold,
teristics; qualitative chemical information was obtained dry or steam autoclave sterilization by Smith et al.
with X-ray spectrometry to indicate oxide prevalence (1992). A transverse load test, tensile strength and
and organic contamination of the wires. Unused Nitinol corrosion resistance test was carried out on 40 wires
wires exhibited large variations in surface texture with of each type used clinically for 1–6 months and on
an undulating ‘bubbling’ or mottled ‘caked’ appearance In five wires in an as received condition. There were no
comparison, stainless steel wires were generally smoother, clinically significant differences between the new or
but showed small metallic prominences. Obvious pits previously used NiTi wires.
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