NICKEL TITANIUM

ALLOYS

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 Contents
• Introduction
• Basic Concepts
-Phase transformation terminlogies
- Typical loading and unloading behaviour of NiTi.
-Hysteresis
• Classification of Nickel Titanium Compounds
• Nickel Titanium Wires
-Properties
-Mechanism of superelasticity
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• Chinese NiTi.
• Japanese NiTi
• Thermoelastic NiTi
• Copper NiTi
• NITRIDING
• Applications of NiTi
• Intraoral Aging of NiTi
• Conclusion
• References

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 INTRODUCTION
• Ni Ti alloy was discovered in early 1960s by William F. Buehler,
a research metallurgist at the Naval Ordnance Laboratory in
Silver springs, Maryland.

• Key discovery occurred in 1962, when a binary alloy

composed of equi-atomic nickel and titanium was found to
exhibit a shape recovery effect when heated after being
mechanically deformed.

• Ni-Ti alloys showed a large recoverable strain value when

compared to other binary, ternary or quaternary shape
memory alloy systems.

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• The physical performance of the Ni-Ti alloy made it a
landmark discovery, and the range of commercially viable
applications that have been found for the materials is proof of
the importance of the nickel-titanium shape memory alloys.

• Buehler’s preliminary results led to development of the first

Ni Ti orthodontic alloy 55% nickel and 45% titanium by
pioneers such as Andreasen and his colleagues in 1972.

• The Unitek Corporation licensed the patent [1974] and

offered a stabilized martensitic alloy (M-NiTi) that does not
exhibit any shape memory effect (SME) under the name,
Nitinol.

• Nitinol – Ni Ti Naval ordnance laboratory.

• It is a stabilized form of the alloy in which work hardening has

abolished the phase transformation 5
• This alloy has low elastic modulus and high range

• The nickel-titanium wires contain approximately

equiatomic proportions of nickel and titanium, and
are based upon the intermetallic compound NiTi
(sometimes written as TiNi).

• Examination of the binary phase diagram reveals that

some deviation from stoichiometry is possible for
NiTi.

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7
 BASIC CONCEPTS ABOUT NICKEL
TITANIUM ALLOYS
1. ACTIVE :-
A term that is used to describe an alloy that is
capable of undergoing its anticipated phase
transformation.

2. PASSIVE :- An alloy that is incapable of undergoing its

anticipated phase transformation because extensive
plastic deformation has suppressed the transition.

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AUSTENITE :-
High temperature phase of Nickel titanium alloys is
called Austenite . Like many ferrous alloys this
austenite can transform to Martensite. It has got
Face centered(Hexagonal Closed Packed). It is the
stronger, higher temperature phase present in NiTi.

MARTENSITIC TRANSFORMATION :-
Process of phase transformation which is
DIFFUSIONLESS, occuring from within and without
any chemical change which results in transformation
of Austenite (parent phase) to Martensite following
rapid cooling. It has got Body Centered(cubic or
tetragonal) More deformable, lower temperature
phase present in NiTi.

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TWINNING :- In certain metals, deformation
occurs by twinning.

It refers to a movement that divides the lattice into

two symmetric parts; these parts are no longer in the
same plane but rather at a certain angle.
e.g., :- NiTi alloys are characterized by multiple
rather than single twining throughout the metal

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• The resulting structure is caused by a reversible Bain
transformation [a rearrangement of atoms in the new phase],
which is responsible for the alloy’s “Shape Memory” and
Superelasticity, properties that derive from the twinning-
detwinning mechanism.
When these alloys are subjected to higher temperature.

DETWINNING OCCURS

Alloy reverts to its original shape.
(SHAPE MEMORY EFFECT).

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 Phase transformation terminologies
Shape Memory: The ability of certain alloys to return to
a predetermined shape upon heating via a phase
transformation.

Af Temperature: The temperature at which a shape

memory alloy ( SMA ) finishes transforming to
austenite upon heating.
Ap Temperature: The temperature at which the SMA is
about 50% transformed to Austenite upon heating.

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As Temperature: The temperature at which the SMA
starts transforming to Austenite upon heating.
Mf Temperature: The temperature at which a SMA
finishes transforming to Martensite upon cooling.
Mp Temperature: The temperature, at which a SMA is
about 50% transformed to Martensite upon cooling.
Ms Temperature: The temperature at which a SMA starts
transforming to Martensite upon cooling.
Hysteresis: The temperature difference between a phase
transformation upon heating and cooling. In NiTi alloys,
it is generally measured as the difference between Ap
and Mp.

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 Af temprature : Most important marker.
To exploit super elasticity to its fullest potential, the
working temperature of orthodontic appliances
should be greater than Af temperature.
Phase Transformation: The change from one alloy
phase to another with a change in temperature,
pressure, stress, chemistry, and/or time.
R-phase: A phase intermediate between Martensite
and Austenite that can form in NiTi alloys under
certain conditions.
Thermoelastic Martensitic Transformation: A
diffusionless, thermally reversible phase
transformation characterized by a crystal lattice
distortion. 15
Superelasticity:
• The springy, “rubber like” behaviour present in NiTi
shape Memory Alloys at temperatures above the Af
temperature. The superelasticity arises from the
formation and reversal of Austenite.

• Part of the unusual nature of a superelastic material

like A-NITI is that its unloading curve differs from its
loading curve (i.e.,the reversibility has an energy loss
associated with it [hysteresis]).

• This means the force that it delivers is not the same

as the force applied to activate it.

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Typical Loading And Unloading
Behavior Of Superelastic NiTi.

Stress strain diagram of alloy

with superelastic behaviour

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• Superelastic compounds generally present a
high stiffness in the initial segment of the
slope of the stress-strain graph when the
deflection of the wire is still minimum.

• The initial activation force required for

austenitic NiTi can be 3 times greater than the
force required to deflect a classic work
hardened martensitic wire (nitinol).

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19
Stainless steel Nickel Titanium

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 Hysteresis
• There is a difference in the transformation
temperatures upon heating from martensite to
austenite and cooling from austenite to martensite,
resulting in a delay or “lag” in the transformation.

• This difference known as the transformation

temperature hysteresis, is generally defined as the
difference between the temperatures at which the
material is 50% transformed to austenite upon
heating and 50% transformed to martensite upon
cooling.

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• For NiTi Alloys, the difference between Mp and Ap is
25-50C.

• Thus Nitinol transformations exhibit thermal

hysteresis, Ms  Af and Mf  As.

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Martensitic transformations do not occur at a precise
temperature but rather within a range known as temperature
transition range(TTR).

Range for most binary NiTi alloys  40 - 60 C.

Transformation from Austenite to Martensite can occur by.

 Lowering the temperature.
 Applying stress (Stress induced Martensite) SIM.

• When the alloy is cooled below the TTR it can be plastically

deformed, but when it is heated again the original shape is
restored. This property is called “THEMO ELASTICITY”.
•
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EFFECTS OF ADDITIONS AND IMPURITIES ON
TTR :-
Adding a third metal can lower the TTR
 to as low as - 330 F ( - 200 C).
 Narrow the difference b/w cooling and heating
(Narrow Hysteresis).
For thermally activated purposes most common third
metals are Cu and Co because.
 Reduce the hysteresis
 Bring TTR close to body temperature.

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 CLASSIFICATION OF NITI COMPOUNDS:
• I. Based on Transformation Temperature Ranges (
Waters,1992)
• Group 1: Alloys with TTRs between room
temperature and body temperature [Active
Martensite].

• Group 2: Alloys with TTR below room temperature

[Austenite active]

• Group 3: Alloys with TTR close to body temperature,

“which by virtue of the shape memory effect spring
back to their original shape when activated by body
heat”.

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• More recently Evans and Durning introduced an even
more comprehensive classification of orthodontic
alloys, dividing them into 5 groups.
•
• PHASE 1, including alloys like gold and stainless steel,
• PHASE 2, stabilised
• PHASE 3, superelastic active austenitic
• PHASE 4, thermodynamic active martensitic
• PHASE 5, graded thermodynamic

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 Nickel Titanium Wires
• CONVENTIONAL NITINOL - Original alloy - 55%
Nickel, 45% Titanium ratio of elements.
To modify mechanical properties and transition temp
1.6% Cobalt was added to it .

CRYSTAL STRUCTURE:
- Stabilized Martensitic form.
- No application of phase transition effects.

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 PROPERTIES
1. Springback and Flexibility
Most advantageous properties of Nitinol are Good
Springback and Flexibility.
Low force per unit of deactivation – that is low
stiffness.

Nitinol wires have greater springback and larger

recoverable energy than Stainless Steel or -Ti when
activated to same extent. High spring back is useful
in circumstances that require large deflections but
low forces.

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2. Spring Rate / Load Deflection Rate:
• Load deflection rate of Stainless Steel is twice that of
Nitinol.
• Clinically this means that for any given malocclusion
nitinol wire will produce a lower, more constant and
continuous force on teeth than would a stainless
steel wire of equivalent size

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3. Formability : Nitinol has poor formability.
Therefore best suited for preadjusted systems.
• Bending also adversely effects springback property of this
wire.

• Cinch backs distal to molar tubes can be obtained by flame

annealing the end of wire. This makes the wire dead soft and
it can be bent into the preferred configuration.

• A dark blue color indicates the desired annealing

temperature. Care should be taken not to overheat the wire
because this makes it brittle.

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4. Shape Memory:
Andreasen and Morrow described the “shape
memory” phenomenon as capability of wire to
return to a previously manufactured shape when it is
heated through TTR.

Ironically the first 50 : 50 composition of Ni and Ti

was shape memory alloy (SMA) in composition only.

Nitinol alloy is passive.

SME had been suppressed by cold working the wire
during drawing to more than 8 – 10%.

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5. Joinability:
Not joinable
Since hooks cannot be bent or attached to Nitinol, crimpable
hooks and stops are recommended for use.

6. Friction:
Garner, Allai and Moore (1986) and Kapila et al (1990):
Noted that bracket wire frictional forces with nitinol wires are
higher than those with SS wires and lower than those with -
Ti, in 0.018 inch slot.
In 0.022 inch slot – NiTi and -Ti wires demonstrated similar
levels of friction.
Although NiTi has greater surface roughness Beta –Ti has
greater frictional resistance

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CLINICAL APPLICATIONS:
Levelling and Aligning:
Nitinol wire is much more difficult to deform during handling
and seating into bracket slots but is easier than Stainless Steel
arch wires.

- Reduces loops formerly needed to level dentition.

- Can be used for longer periods of time without changing.

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Torque can be controlled early in treatment because successive
arch wires fit with precision and ease.

- Rectangular Nitinol inserted early in Rx – accomplishes

simultaneous leveling, torquing and correction of rotations.

B
- ite opening using RCS.
(Reverse Curve of Spee)

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ADVANTAGES :
- Fewer arch wire changes.
- Less chair side time.
- Less patient discomfort.
- Reduction in time to accomplish rotations.

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LIMITATIONS:
- Poor formability.
- Poor joinability.
- By its very nature nitinol is not a stiff wire which
means that it can easily be deflected. Low stiffness of
nitinol provides inadequate stability at completion of
treatment. Such stability is often best maintained by
using stiffer Stainless Steel wires tailored to the
desired finished occlusion.
- Tendency for dentoalveolar expansion.
- Expensive.

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Conventional Nitinol is available as
- Nitinol classic - Unitek corporation.
- Titanal - Lancer pacific.
- Orthonol - Rocky mountain
orthodontics.

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PSEUDOELASTIC NITINOL:
In the late 1980s, new Nickel titanium wires with an Active
Austenitic grain structure appeared.

Stress Induced Martensitic Transformation : (SIM)

Occurs because of phase transition in grain structure from
Austenite to Martensite, in response not to temperature
change but applied force.

This transformation is mechanical analogue of thermally

induced shape memory effect. ,the Austenitic alloy undergoes
a transition in internal structure in response to stress without
requiring a significant temperature change.

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This group is also referred to as A-NiTi.
This group includes :
- Chinese NiTi.
- Japanese NiTi (Sentinol)
- 27C superelastic Cu-NiTi.
In Austenitic active alloy both Martensite and Austenitic phases
play an important role during its mechanical deformation .

• A material with an Active Af of about 15C will exhibit good

superelasticity upto about 65C which means that the
material will exhibit good superelasticity at both room
temperature and body temperature

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 CHINESE NI TI
Developed by Dr. Tien Hua Cheng and associates for orthodontic
applications at the General Research Institute for Non ferrous
metals in Beijing, China. Reported by Burstone in 1985.
In 1978 : Furukawa Electric Co. Ltd. of Japan produced a new type
of Japanese NiTi alloy.
In 1986 : Miura et al reported on Japanese NiTi

Superelasticity is produced by stress, not by temperature change

and is called stress induced Martensitic transformation (SIM).

Provides light continuous force for physiologic tooth movement

Spring Back :
At 80 of activation.
Chinese NiTi wire has :
- 1.4 times the springback of Nitinol wire.
- 4.6 times the springback of SS wire. 40
• Stiffness of Chinese NiTi is 36% that of Nitinol wire.

• Temperature dependent effects are clinically

insignificant.

• Chinese NiTi deformation is not particularly time

dependent unlike nitinol wire, will not continue to
deform a significant amount in mouth between
adjustments.

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• Other Super Elastic NiTi wires
3M Unitek: Nitinol Super Elastic
American Orthodontics: Titanium Memory
Wire: Available in two force levels : Force I –
low force,Force II – high force.
Ortho Organizers: Nitanium
Masel Orthodontics: Elastinol

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• ADVANTAGES:
Constant force over wide range of deflection.

Low stiffness.

High springback.

More effective in initial tooth alignment.

Less patient discomfort.

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LIMITATIONS OF SUPERELASTIC NiTi:
Cannot be soldered or welded.

Poor formability.

Tendency for dentoalveolar expansion.

“Travels” around the arch.

Expensive.

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 Thermoelastic nitinol
Thermal analog of pseudoelasticity in which
martensitic phase transformation occurs from
Austenite as temperature is decreased.

This phase transformation can be reversed by

increasing the temperature to its original
value.

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CHARACTERISTICS OF AN IDEAL THERMODYNAMIC
NITINOL WIRE:
1. Dead soft at room temperature so that it can be
tied easily.

2. Instantaneously activated by heat of mouth.

3. Able to apply clinically acceptable orthodontic

forces.
4. Once fully activated would not be affected further
by increased heat in the mouth.

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 COPPER NiTi
Invented by Dr. Rohit Sachdeva & Suchio Miyazaki .

COMPOSITION : Quaternary alloy containing.

* Nickel * Copper (5 – 6%)
• Titanium * Chromium (0.2 – 0.5%)

Copper:
- Increases strength
- Reduces hysteresis
- these benefits occur at expense of increasing TTR above that
of oral cavity.
Chromium : to compensate for the above mentioned unwanted
effect 0.5% chromium is added to return TTR close to oral
temperature
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TYPES OF CU-NITI:
1. Type I Af 15C.
2. Type II Af 27C
3. Type IIIAf 35C
4. Type IV Af 40C

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49
 Chill Spray
• Facilitates adjustments or fitting of Ni
Ti orthodontic archwires,
springs,appliances, etc.

• Chills to -620º F/-520 ºC.... puts Niti

into its soft martensitic state (below
the Ms of the wire)

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ADVANTAGES OF Cu-NiTi OVER OTHER NiTi
Alloys:
1. Cu – NiTi generates more constant force over long
activation spans.
2. More resistant to permanent deformation.
3. Exhibits better springback properties.
4. Exhibits smaller drop in unloading forces (reduced
hysteresis).
Provides precise TTRs at 4 different levels – Enables
Clinician to select archwires on a case specific

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• Bioforce Sentalloy –
• A Graded Thermodynamic Wire.

• The heat treatment of selected sections of the archwire by

means of different electric current delivered by electric pliers
modified the values of the deactivation forces by varying the
amount of austenite present in the alloy.

• Similar manufacturing procedures have been perfected to

produce wires such as Bioforce Sentalloy (GAC) that are able
to deliver selective forces according to the needs of the
individual dental arch segments

• BioForce (GAC) offers 80 grams of force for anteriors and up to

320 grams for molars
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 NITROGEN COATED ARCHWIRES:

Implanting Nitrogen on surface of NiTi alloys by Ion

implantation process – NITRIDING.
Advantages:
- Make Titanium more esthetically pleasing giving it
gold like aspect.
- Hardens surface.
- Reduces friction.
- Reduces Nickel release into mouth.
e.g : Bioforce Ionguard - 3m Nitrogen coating.
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The IONGUARD process actually alters the wire’s
surface to provide a dramatically reduced
coefficient of friction for sliding mechanics that
are better than the same size stainless steel wire
and half the friction of competitive NiTi wire.

It also seals the occlusal surface of the wire to

eliminate breakage and reduce nickel leaching.

While the IONGUARD process alters the surface

of the wire, none of the wire’s unique properties
is changed.

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 Nitinol Total Control .A new Orthodontic alloy.
• TODD A. THAYER, KARL FOX,ERIC MEYER ( JCO1999)
developed a new pseudo-superelastic nickel titanium,alloy,
Nitinol Total Control,
• Accepts specific 1st-, 2nd-, and 3rd-order bends while
maintaining its desirable superelastic properties.

• Combines the ability of superelastic nickel titanium to deliver

light, continuous forces over a desired treatment range with
the bend ability required to account for variations in tooth
morphology, archform, and bracket prescriptions.

• Frictional and bending tests verify that the force levels

produced by them are within accepted ranges for optimal
tooth movement. Furthermore,wire properties are not
temperature dependent.
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 SPEED System Super Cable

• Archwire designed by combining the

metallurgical benefits of nickel titanium wire with the
mechanical advantages of a coaxial design.
• The result is an archwire that imparts extremely light forces
when subjected to severe deformation.

• approximately 1/3 the force of .013” CuNiTi

approximately 1/2 the force of .014”
Heat Activated Nickel Titanium

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 References
• Orthodontics: Current principles and Techniques;
GraberVanarsdall, Vig 4th Edition, Elsevier.

• Santoro M, Nicolay OF, Cangialosi TJ.: Pseudoelasticity and

thermoelasticity of nickel titanium alloys: A clinically
oriented review. Part I: Temperature transitional ranges.
AJODO 2001; 119:587-593

• Brantley WA, Eliades T.: Orthodontic materials-scientific and

clinical aspects. New York: Thieme;2001. Page – 80 – 103

• TODD A. THAYER, KARL FOX,ERIC MEYER: Nitinol Total

Control .A new Orthodontic alloy.JCO1999; 27 (10), 563-
567.
• Waters NE: Orthodontic products update. Superelastic
nickel titanium wires. BJO; 1992;19:319-322.
• Arndt WV: Nickel Titanium Palatal expander. JCO 1993, 27;
129-137
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THANK YOU…
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