NiTi based Shape Memory Alloys and its Medical Applications

Seminar Presentation

By Divyanshu Singh (08011002) Aniket Patni (08011018)

Content
NiTi Shape Memory Uniqueness of Shape Memory Alloys Superelasticity Martensitic Transformation Transformation Thermodynamics Transformation Kinetics Stability in Material Response Macroscopic Characterization of SMAs Medical Applications of Nitinol

NiTi
Nickel titanium, also known as Nitinol, is a metal alloy of nickel and titanium, (where Ni 50 to 51% nickel by atomic percent i.e. 55 to 56% weight percent ) Nitinol alloys exhibit two closely related and unique properties:
Shape memory refers to the ability of nitinol to undergo deformation at one temperature, and then recover its original, undeformed shape upon heating above its Transformation Temperature - To". Superelasticity (also called pseudoelasticity) Shape Recovery with enormous Elasticity occurs some 10-30 times that of ordinary metal.

Shape Memory
A shape memory alloy (SMA, smart metal, memory metal, memory alloy, muscle wire, smart alloy) is an alloy that "remembers" its original, cold-forged shape: returning the pre-deformed shape by heating. Shape Memory Effect
Fig 1: Schematic of phase transformation in SMAs; (a)-(b)-(c) is a typical shape memory cycle. (a)-(c) under stress cycling represents Superelastic cycle; (a)-(c) under thermal cycling represents another shape memory path

Shape Memory
Mf is the temperature at which the transition to martensite completes upon cooling. As and Af are the temperatures at which the transformation from martensite to austenite starts and finishes.

Fig 2 (T) represents the martensite fraction. The difference between the heating transition and the cooling transition gives rise to hysteresis where some of the mechanical energy is lost in the process.

Classification Shape Memory Alloys

Two broad classes of SMAs : Thermally Activated and Magnetically Activated Two common effects are one-way and two-way shape memory

Fig 3 - The procedures are very similar: starting from martensite (a), adding a reversible deformation for the one-way effect or severe deformation with an irreversible amount for the two-way (b), heating the sample (c) and cooling it again (d)

Uniqueness of Shape Memory Alloys

The special property that allows shape memory alloys to revert to their original shape after heating is that their crystal transformation is Fully Reversible. Diffusionless Transformation: A reversible transformation does not involve this diffusion of atoms, instead all the atoms shift at the same time to form a new structure whereas most crystallographic transformation composition changes locally.

Superelasticity
Upon loading Stress Induced Martensite (SIM) is directly produced from pure austenite phase leading to large macroscopic strains which are recovered by unloading when the temperature is above Af. Shape memory alloys has the high level of recoverable plastic strain that can be induced. The maximum recoverable strain these materials can hold without permanent damage is up to 8% for some alloys

Fig.4 Superelasticity effect; (a) load path a-b-c-d-e-a on stress-temperature diagram; (b) stress-strain hysteresis response

Martensitic Transformation
Nitinol's unusual properties are derived from a reversible, solid state phase transformation known as a martensitic transformation. At high temperatures, nitinol -simple cubic crystal structure austenite (also known as the parent phase) At low temperatures, nitinol-more complicated B19 structuremonoclinic-martensite

Fig.5 Austenite and Martensite structures of the NiTi compound

Martensitic Transformation
Austenite transforming to lens shaped or plate like regions with body centered cubic lattices or body centered tetragonal lattices -Martensites without atomic diffusion are called -Martensitic Transformations or simply, - MTs. The Martensitic Transformations properties: 1. The martensite phase is a substitutional or interstitial solid solution. 2. The transformation is diffusionless. 3. The transformation is accompanied by shape changes (or surface relief) of a definite value - because the shape changes accompanying the transformation are of a definite value and is typically taken as proof that the transformation mechanism involved is shearing deformation.
Fig 6 Formation of Surface Relief and Bending of Scratch Line Accompanying Martensitic Transformation

Martensitic Transformation
4. An M crystal has a specific-habit plane. 5. There is a definite orientation relationship between the P and M phase lattices. 6. Lattice defects necessarily exist in the M crystal which leads to Complimentary Slip and Shear Twinning

Fig 7 Lattice Deformation and Complimentary Slip Shear and Twinning Shear (dotted lines show the actual shape change)

Transformation Thermodynamics
Driving Force: G < 0
Assume a lens shaped M crystal with radius r and average thickness 2t (r >> t) has nucleated. Then, Interface Energy = 2r2 2r2 is the approximate surface area is the interface energy per unit area. The elastic strain energy is = r2t(At/r) = rt2 A r2t ~ volume and A(t/r) is the elastic strain per unit volume Twinning or slip deformations in the form of lattice invariant strain in the M crystal, then by analogy with elastic energy, r2t(Bt/r) = rt2B G = r2tgc + 2r2 + r2t(A + B) Where gc is the change in the chemical free energy per unit volume
Fig 8 Temperature Dependence of the Chemical Free Energies of the Parent and Martensitic Phases and their relations to Martensitic Transformation

Transformation Thermodynamics
Driving Force: G < 0 The total free energy can be written G(T)PM = gc PM(T) + (gnc PM) + gs PM For the reverse transformation, the change is, G(T)MP = gc MP (T) + (gnc MP) + gs MP gc is the change in the chemical free energy and gnc is the increase in the non-chemical free energy (considering only the elastic energy accumulated in the thermoelastic transformation). The energy term gs corresponds to the forces resisting either the growth and shrinkage of existing M crystals or the creation and annihilation of new M crystals.

Nitinol Parameters
The degree of supercooling = 50 100oC Transformation Temperature To = 30oC

Transformation Kinetics
Martensitic Transformation are athermal transformation as they dont start at point where G = 0; they require a certain undercooling to Mf or superheating to As. Thermodynamically, MT in SMAs is classified as either a weak first order or a second order transformation Thermo-elastic Transformation:

where, is the stress, H, the change in enthalpy due to transformation and 0, the total inelastic strain, 0 is the molar volume, , the change in entropy due to transformation

Stability in Material Response

Under repeated loading, the material behavior is said to be stable, if the hysteresis for each load cycle is stable (shows no drift) this is high fatigue resistance of Nitinol millions of cycle and no drift.

Stability is desirable from a device or an application perspective and hence special thermomechanical treatments are imparted to the material to achieve the same. For higher loads, a certain number of additional cycles are necessary before stabilization occurs. Such transformation behavior can be interpreted as imperfect memory which needs multiple cycles to become perfect.

Stability in Material Response

Fig 9: Different inner or partial loop behavior; (a) return point memory behavior in a commercially available NiTi ; (b) Schematic sink point behavior.

Macroscopic Characterization of SMAs

Differential Scanning Calorimetry (DSC) The transition temperatures and the enthalpy of transformation (H) associated with MP (heating) and PM (cooling) transformations are determined. H is measured as the area under the transformation peaks during the heating and cooling cycles.

Fig 10: Heat flow vs. temperature trace in DSC for SMAs (a) without R-phase and (b) with R-phase. Transformation temperatures are identified by drawing tangents as shown.

Macroscopic Characterization of SMAs

Stress-strain-temperature tests Isobaric Tests Tangents are drawn to the heating and cooling segments to obtain the transformation temperatures (Ms, Mf, As and Af). Another parameter that is obtained from this test is the amount of transformation strain.

Fig 11: Strain-temperature hysteresis at 100 MPa

stress for a commercially available NiTi

Macroscopic Characterization of SMAs

Stress-strain-temperature tests Isothermal Tests Critical transformation stresses for both forward and reverse transformation are obtained from this test. The transformation strain can also be determined from this test.

Fig 12 Stress-strain response and tangents drawn to determine critical transformation stresses for a commercially available NiTi

Medical Applications of Nitinol

Applications That we discuss today

Inferior Vena Cava Filter Intravascular Stents Orthopaedic Applications

Inferior Vena Cava Filter

Medical Complication Treatment Techniques Advantages & Properties of Nitinol making it suitable for use as Filter

Medical Complication
Pulmonary embolism occurs when a fragment of a blood clot detaches and reaches the lungs via the veins. It thus causes shortness of breath, pain during inspiration and may ultimately lead to heart failure and death

Treatment Techniques
Administering anti-coagulant drugs and surgically removed. Closure of Inferior Vena Cava by external means such as clips, ties etc causing the blood to reach the heart through other pathways which are smaller in size and do not allow the passage of emboli.

Deployment of Filter which traps the emboli where they dissolve over time.

Human Circulatory System

Fig 13 Human Circulatory System

Deployment of Filter

Fig 14 Diagram for Delivery System for Filter

Deployment of Filter
Inferior Vena Cava Filter

Fig 15 Nitinol Filters

Deployment of Filter
Filter is straightened in ice-cold water and placed inside catheter. The catheter travels over the guidewire to reach the desired location. A constant flow of chilled saline solution is maintained to avoid the filter from taking shape inside the catheter. At the desired location the straightened wire is pushed out where it takes the shape of the filter.

Deployment of Filter

Fig 16 Deployment of Filter

Properties of Nitinol making it Suitable for Use

Shape Memory Effect and Thermal Deployment Biocompatibilty Magnetic Resonance Compatibility

Thermal Deployment
Leads to the introduction of filter via a smaller entry hole reducing the trauma and risk of bleeding for the patient Complex shapes of filters can be placed at the deployment site using the shape memory effect.

Biocompatibilty
Nickel is carcinogenic that is cancer inducing Titanium is a biocompatible material Titanium however forms a passive layer of Titanium oxide on the surface of nitinol making it biocompatible Titanium oxide deters corrosion of the surface and prevents the nickel from coming in direct contact to the body parts.

Magnetic Resonance Compatibilty

A desired characteristic of the filter is its possibility to be tracked precisely inside the body. Nitinol being non-ferromagnetic and less sensitive to magnetic resonance yields clear images and prevents the use of X-rays or other forms of radiation that might trouble the body.

Intravascular Stents
Medical Complication Treatment Techniques Properties of Nitinol making it suitable for Use

Fig 17 Intravascular Stent

Medical Complication
Occlusion (blockage) or stenosis (narrowing) of blood vessel or heart valve. Angioplasty is the technique used to treat the above ailment

Treatment Techniques
A stent is deployed at the site of constriction where it is expanded to maintain proper gap between the walls of the blood vessel thus ensuring proper flow of blood. Deployment of Balloon Expandable Stent Deployment of Self Expanding Stent

Balloon Expandable Stent

A balloon tipped catheter is passed over the guidewire until it reaches the occlusion or stenosis. The cylindrical shaped balloon is then inflated to widen the blocked vessel Subsequently the wire, catheter and the balloon are withdrawn. This method suffers from high rate of Restenosis

Self-Expanding Stent
These are permanently implanted cylinders at the site of the occlusion to support the walls of the vessel. The stent is shape set in the open condition and then compressed and inserted into the delivery catheter at a temperature below TTR where it is kept cool by passing cold saline around it.

At the occlusion site it is pushed out where it self expands and the catheter and the guidewire are withdrawn.

Fig 18 Intravascular Stent in the internal carotid artery

Properties that make Nitinol Ideal for this Application

Shape Memory Effect or Thermal Deployment Dynamic Interference Hysteresis Loop Biocompatibilty Magnetic Resonance Compatibility

Shape Memory Effect or Thermal Deployment

Fig 19 Stress-Strain Curve for Nitinol

Dynamic Interference
When using balloon expandable stainless steel stent after the balloon is deflated there is spring back causing the stent to revert to a smaller undeformed shape. This is called acute recoil and can damage the vessel as it requires the expansion of stent to large dimensions. Because of this temporary spasm the stent may not follow the vessel wall. The nitinol stent however continues to exert a constant force until it reaches the preset diameter.

Hysteresis Loop
Ideally a stent should resist crushing during normal physiological processes (radial resistive force) and also exert a small outward force on the wall during recovery (chronic outward force). In the hysteresis curve the upper plateau represents the force required to deform the stent while the lower plateau indicates the force exerted during selfexpansion.

Properties making Nitinol Ideal for this Application

Biocompatibility Magnetic Resonance Compatibility

Orthopaedic Applications
Treatment of Scoliosis Surface Arthroplasty Treatment of Fractures

Treatment of Scoliosis
Scoliosis is a deformity of spine. In scoliotic backs the spine is seen to have one or more lateral curvatures. These curves may vary in severity and can cause disability or internal organ difficulties. The treatment involves the placement of a distraction rod to the spine which exerts a continuous force on the spine and realigns it to its correct position.

Scoliosis

Fig 20 Scoliosis

Treatment Of Scoliosis
Hooks are attached to the laminae of the vertebrae above and below the curve to be corrected. The spine is then externally straightened and a distraction rod attached to the hooks. In conventional treatments not employing Nitinol the correction force would decrease by upto 30% over time and thus required a second surgery. Nitinol however exerts a constant force over large strain ranges and eliminates a second surgery as the alloy could be externally heated to obtain its preset shape and exert the same force as originally applied.

Surface Arthroplasty
Knee replacement or Knee Arthroplasty is a surgical procedure to replace the weight bearing surfaces of the knee joint to relieve the pain. It involves the placement of a corrosion resistant cup on the weight bearing surface of the knee joint.

Surface Arthroplasty
At zero degree the hooks are deformed so that the cups can be placed on top of the knee joint. Once set the hooks revert back to their original position as a result of the warming created by the body temperature and in doing so clamps the cup to the bone

Fig 21 Diagrammatic representation of a Ni-Ti cup used in Surface Arthroplasty

Treatment of Fracture
The treatment of fractured bones employs wavy staples which are elongated at zero degree along their U section and placed within the pre-drilled holes in the bones. Upon warming the wavy section returns to its original shape and thus produces a compressive force between the two subject bones.

Treatment of Fracture

Fig 22 Diagrammatic representation of Ni-Ti orthopaedic staples a)Before deformation b)After deformation at the time of implant c)Return to the original shape causing a compressive force

Fig 23 Schematic of Compressive Staple used

Thank You