METALLIC BIOMATERIALS

Contents
1. Introduction

and History 2. Metallic Alloys 3. Fabrication 4. Drawbacks 5. New Directions

History
Preserved skeletons show that bone
diseases have afflicted man since before recorded history. The use of materials as constituents of surgical implants is not new. One of the rst used biomaterials were metallic biomaterials in the fabrication of surgical implants many decades ago.

 Substitutions of bone parts for repairing

damaged portions of the human body have been recorded since the pre-Christian era. Bronze or copper were utilized in situations requiring the assembly of fractured bone parts.

Use of gold plates to x teeth

First bone plate (steel with Nicoating)

First bone plate of Valloyed steel of high strength

500 BC 17th Century

1866

1893

1912

Use of wire from iron, gold & bronze for suture & wounds 1920

Development of screws & plates from steel

1938

1946

Development of Cr-Ni and Cr-Ni-Mo steels (stainless steels)

First prosthesis for total hip replacement

Commercial production of Ti and Ti-alloys

What is a metallic biomaterial ?

Metallic biomaterials are metal implants
that are planted inside the body specially in bone replacement eld due to their superior load bearing, mechanical & electrical properties. These favorable properties (good fracture resistance, electrical conductivity, formability) are related to the metallic inter atomic bonding that characterizes this class of material.

Examples of metallic biomaterials

Classication of Metallic Biomaterials

Titanium based alloys Stainless steels Cobalt based alloys Shape memory alloys Combinations of metallic biomaterials

A small idea about how it works

Schematic illustration of a metallic hip implant component in the femur showing the direction and concentration of lines of force acting during loading. The stiffer implant component acts to shield the bone.

So where are they in the body ?

Metallic materials are used in biomedical
devices for various parts of the human body like articial joints, bone xation devices, dental implants, orthodontic wires, crowns, and bridges, stents, clips, and articial hearts.

Current Applications
Temporary
! Surgical implants ! Wires, plates, screws for fixation of broken bone

Permanent
! Implants (teeth, spine cage) ! Joint implants ! Aneurysms clips ! Aneurysms coils ! Stents ! Screws

Implanting Criteria
1. 2. 3. 4. 5. 6. 7. 8.

Appropriate tissue-material interface Non-toxic Non-corrosive Adequate fatigue life Proper design Proper density Relatively inexpensive Elastic and mechanical properties comparable to those of bone

Design Considerations
Matching mechanical properties of tissue with mechanical properties of metal

Have to consider how the metal may fail inside the body

A material may fail inside the body by:

Corrosion

Wear

Fatigue

What got wrong ?

A major factor impeding success was the
accumulation of toxic copper ions in the liver, brain, and other body tissues once the implant had completely dissolved.

An example of a poisoned tissue

Metallic Alloys Used

An Overview on A Few

Major Metallic Alloys

Vanadium-Steel Alloys Stainless Steel Alloys Cobalt-Chromium Alloys Titanium Alloys

Vanadium-Steels

Vanadium-Steels

The rst metal produced specically for human use Contained: up to 0.5% V, 0.4-0.5% C, 1.1-1.5% Cr. Was Used for Sherman plates (fracture plates)

Vanadium Steels

Its corrosion resistance was inadequate invivo This caused the release of harmful material that may kill the surrounding tissue.

Vanadium Steels

Its corrosion resistance was inadequate invivo This caused the release of harmful material that may kill the surrounding tissue.

Stainless Steels
Just like old times!

Stainless Steels

Replaced Vanadium Steels. Stainless Steels are: Fe+low C%+17% Cr+11% Ni+2% Mo Have highest susceptibility for crevice corrosion (among all other alloys). Still used for fracture repairs (Fracture Screws, Plates, and Hip Nails).

Stainless Steel Alloys

AISI 302 AISI 316 AISI 316L

AISI 302

The rst stainless steel used. Stronger and more resistant to corrosion than V-Steel. in 1948, it was considered ideal for orthopaedic applications

AISI 302
Element C Cr Mn Ni P Si % 0.15 17-19 2 8-10 0.045 max 1

AISI 302

Disadvantages: - Too high C% for human body. - Relatively low corrosion resistance to biouids.

AISI 302
Bye Bye!

AISI 316

It had better corrosion resistance to salt water due to added Mo. It had lower carbon content. in the 1950s, it was modied to give the AISI 316L.

AISI 316
Element C Cr Mn Ni P Si Mo % 0.08 16-18 2 10-14 0.045 max 1 2-3

AISI 316L

Same as 316 but with lesser C% (0.03 instead of 0.08% max) Better corrosion resistance. Less probability for sensitization

Stainless Steels: Drawbacks

Relatively low corrosion resistance (even the 316L can corrode in highly stressed, Oxygendepleted regions such as under the fracture screws). Used only for Temporary fracture implants (may need 2nd surgery).

Cobalt-Chromium Alloys
Nice and Shiney!

Co-Cr Alloys

Co-Cr solid solution of up to 65% Co. Higher corrosion resistance than StSt (due to Cr). Higher Youngs Modulus than StSt. Enhanced Strength (Solid Solution Strengthening due to Cr)

Co-Cr Alloys

Cast Co.Cr.Mo alloy (ASTM F75) Wrought Co.Cr.W.Ni alloy (ASTM F90) Wrought Co.Ni.Cr.Mo alloy (ASTM F562) Wrought Co.Ni.Cr.Mo.W.Fe alloy (ASTM F563)

Co-Cr Alloys

Castable CoCrMo

Most Clinically wear resistant metallic biomaterial (due to carbides formed during solidication). Its Mo causes the grains to be ner. Excellent corrosion resistance. Used for decades in dentistry and relatively recently in articial joints.

Cast CoCrMo alloy: Fixation

Either:

Using Acrylic Bone Cement; Sintering CoCrMo powders to the bone interface directly; Plasma Spray-Coating the surface with a bioactive material.

Wrought CoNiCrMo

Excellent corrosion resistance. Superior fatigue and high tensile strength. Suitable for long service-life applications without fracture or stress fatigue. Used for stems of prosthesis for heavilyloaded joint (ex: hip and knee). It has poor frictional properties with itself and other materials.

Co-Cr Alloys: Drawbacks

They have relatively high Youngs Modulus (which may cause stress-shielding). Extensive release of Ni and Co ions may have toxic effects on surrounding tissue and organs.

Interesting Point (IP)

IP #1

Ni-release
The Wrought CoNiCrMo alloy releases Ni ions -----> so does StSt. But: Although StSt has lower Ni %, it has a higher release rate!

Titanium Alloys
The Real Deal

Titanium Alloys

Excellent in-vivo corrosion resistance. (owing to passive oxide layer that rapidly forms). Good fatigue resistance. Lower elastic moduli (100-110 compared with 200-225 GPa of other used alloys). Strong tendency for osseointegration. (wait for it)

Interesting Point
IP #2

Metal-Tissue integration
Metal tissue integration or osseointegration with metals can occur. (Oxide layer is formed)

Metal-Tissue integration
But: this oxide layer may not be homogeneous and thus full osseointegration may not occur. Otherwise: metals are biologically inert.

Titanium Alloys

Used for fracture xation, joint implants, and almost exclusively for endosseos dental implants.

Titanium Alloys

Commercially Pure (CP) Ti Alloys. & Alloys:

( + ) Alloys & Near- Alloys

CP Ti (Alloys)

Not so pure!

CP Ti (Alloys)

Used for endosseous dental implants where osseointegration occurs. Grades III & IV: used for osteosynthesis (fracture repairs and spinal fusion) but not joint replacement due to low fatigue strength and mechanical properties.

 & Alloys

( + ) Alloys

Higher strength (yield, ultimate) than CP Ti. Superior corrosion-fatigue properties. Osseointegration tendency. Examples: Ti6Al4V; Ti6Al7Nb; Ti5Al2.5Fe.

( + ) Alloys

Ti6Al4V:

Excellent corrosion resistance. Can be spray coated or sintered as powder on a substrate. A bioactive material (ex: Bioglass) can be spray-coated on it to insure osseointegration.

 & Near- Alloys

If appropriately processed, can have very low elastic moduli (44-51 GPa for Ti13Nb13Zr, a near -alloy) - increases by annealing. Excellent corrosion resistance. Good formability. High hardenability. better notch sensitivity than( + ) Ti alloys.

Other Metallic Alloys

Nickel-Titanium Alloys Zirconium-Niobium Alloys Tantalum Platinum and Platinum-Iridium Alloys Major Dental Restoration alloys

Nickel-Titanium Alloys
Shape Memory Awesomeness!

 Ni-Ti Alloy: Nitinol

Nitinol is a shape memory alloy. It has good corrosion resistance. Its Martinsitic phase has elastic modulus 28-41 GPa. Ni release makes it a choice for temporary implants.

Interesting Point
IP #3

How can SMAs be properly used in the body?

Glad you asked!

1 way of using SMAs

The original shape is Austenite. Deform or cool it ---> gives Martensite Put it in body ---> heats up with body temp. to give Austenite with original shape again. This original shape pulls or pushed bones or tissue together.

: Nitinol

Applications

Orthopaedics: fracture xation devices. Spinal rods for treatment of scoliosis Cages for use during spinal fusion and even self-locking joint replacement components. Orthodontics: large working range wires during force application for tooth repositioning. SMAs are also used for cardiovascular stents. (pseudo-elasticity)

Zirconium-Niobium Alloys

Zr-Nb Alloys

Zr-Nb alloys, due to ZrO2 layer formed, have:

Corrosion Resistance Wear Resistance Hardness High Reactivity

Zr-Nb Alloys

Used for making orthopaedic components that are primarily intended for compressive loading and resisting wear (such as femoral hip implant and knee implant components)

Interesting Point
IP #4

To crack, or not to crack

Stabilised ZrO2 is a strong ceramic. But: Zr-Nb alloys are better than regular ZrO2 ceramics due to less susceptibility for crack propagation.

To crack, or not to crack

Because: the brittle ZrO2 is reinforced by Zr-Nb alloy.

Tantalum
nally, a pure metal!

Tantalum

It is considered biocompatible (due to Ta2O5 layer formed). Porous Tantalum structure is used for augmentation templates. It is weak but bone grows inside it and takes the load.

Platinum and PlatinumIridium Alloys

Nobel Biomaterials

Pt and Pt-Ir Alloys

Used for electrodes used in electrical stimulation (ex: neuromuscular stimulation or pace-makers) and sensing devices. extreme voltages.

Superior corrosion resistance especially at

Dental metallic implants

Types of alloys used depending on application

Direct llings in teeth (dental amalgams) Fabricating crowns and bridges (noble metal and base metal alloys)

Partial denture framework (base metal alloys) Orthodontic wires and brackets (stainless steel types 302, 303, 304 and 305, CoCrNiMo alloys (Elgiloy), -Ti, and Ni-Ti alloys), (because of their low elastic moduli, high strengths and consequently large working range, a desirable characteristic for this application). Dental implants (CP Ti and Ti6Al4V)

Dental amalgams

Hg added to alloys containing Ag, Cu and Sn plus some other minor elemental additions

Amalgam types

High (Cu >6 wt%) Low (Cu <6 wt%)

Advantages and drawbacks

Advantages Drawbacks

Amalgams in situ formability to the desired shape

Hg toxicity that is still

widely debated up till now while nothing yet has proven to be valid to prevent amalgam from being used.

Dental Casting Alloys (Au-based, Coand Ni-based, Ti-based)

Dental casting alloys are used for making

dental bridges, crowns (with porcelain fused to a metal substrate), inlays, onlays,

Both noble and non-noble (base) metal alloys are used to form these often-complex shapes. As they Require

Sufcient strength, Toughness, Wear resistance, Corrosion resistance Biocompatibility

General Fabrication Steps

General Fabrication Steps

Heat Treatments
Raw metal

Testing

Final metal device

Metal Ore

Solidification

Stock metal Shapes Fabrication

Separation Alloying Purification

Mining Ore separation / concentration Chemical extraction of metal Rening Alloying Casting, Rolling, Forging, Powder Production, heat treating Fabrication Investment casting Grinding Powder metallurgy Surface preparations Nitriding Polishing Cleaning Quality control Packaging Final implant device Preliminary implant device Stock shapes e.g. sheet, tube, bar,plate,powder,wire Metallic raw material in bulk form Mineral Ore

Example

Market

Manufacture of Metallic Implants

Machining

Powder Metallurgy

Investment Casting

Manufacture

Forging

Finishing

Surface Treatments

A variety of methods are required because not all implant alloys can be economically made in the same way.

Example

- Cobalt-based alloys are difcult to be machined so they are fabricated by casting or powder metallurgy. - Titanium is difcult to cast so it is machined.

Surface Treatments!
They improve xation of implants in bones by the application of macro or micro porous coatings on implants or the production of certain degrees of surface roughness.

Surface Treatments!

Sinterng

Flame Spraying

Plasma Spraying

Surface Treatments!

Nitriding

Ion Implantation

Finishing!

Chemical Cleaning

Electrolytically controlled treatments

To remove machining chips or impurities

These steps are important to the overall biological performance of the implant because they affect the surface properties that come in direct contact with the blood and other tissues at the implant site.

Example

The fabrication of ASTM F75!

Material ASTM designation F75 Common trade names Vitallium Haynes - Stellite 21 Protasul Micrograin Zimaloy Composition Wt% 58.9 69.5 Co 27.0 30.0 Cr 5.0 7.0 Mo Max. 1.0 Mn, 1.0 Si, 2.5 Ni, 0.75 Fe, 0.35 C

Co-Cr-Mo

1. The alloy is melted at 1350-1450 0C 2. Poured or pressurized into ceramic molds of the desired shape through sprues, or pathways. 3. Once the metal has solidied into the shape of the mold, the ceramic mold is cracked away.

Investment Casting

This process can produce at least three microstructural that can inuence negatively the implant properties:
A Cobalt rich matrix plus dendritic and grain boundary carbides , cored microstructure can develop due to nonequilbrium cooling.

Relatively large grain size results due to solidification. This decreases the yield strength.

Casting defects as inclusions, macro or micro porosity (due to metal shrinkage upon solidification) may arise.

Polished-etched view of a cast ASTM F75 femoral hip stem. Note dendrites and large grains

In vivo fracture initiated from an inclusion formed during the casting process

Powder Metallurgy
hot isostatic pressing

The ne powder is compacted and sintered together under appropriate pressure and temperature (100 MPa, 1100 0C for 1 hour).Then forged to nal shape.

Finer grain size and a ner distribution of carbides can be obtained.

Drawbacks of metal

Major drawbacks
Nothing is more wonderful than inventing a new material. Scientists always have been proud of inventing new materials.

Any new material must have some drawbacks in the beginning of its invention. But the challenge her is to overcome this drawbacks and try to nd a solution to it.

Wear

Wear is a critical issue for prostheses, implants, and other medical devices Wear may lead to signicant loss of material or failure of a medical device. Relatively small amount of wear can lead to signicant degradation of function for some medical devices The most important two types of wear : adhesive wear and fatigue wear.

Wear

Adhesion wear: it originate from adhesion of two surfaces that are in contact. The contact area is smaller than the appeared contact area.

Fatigue wear: wear mechanism that occurs when a material undergoes cyclic loading. Fatigue wear can be observed in sliding, rolling, or impact wear processes.

Example on wear

Lets study joint prosthesis wear. There are four modes of wear.

Mode 1 wear in a total hip replacement prosthesis occurs between the femoral head and the ace tabular cup. Mode 2 wear may take place between the femoral head and the metal backing of the ace tabular cup. Interaction between metal debris, the femoral head, and the ace tabular cup is an example of three-body wear.

Mode 4 is an articulation between two nonbearing secondary surfaces in prosthesis. Factors affecting wear rate:

The type of motion.

Factors affecting wear rate

The number of cycles of motion.

Clinical practice.

Design

Corrosion
The implanted material is exposed to body uids, such as intercellular uid and blood depending on the surrounding tissue. Body uid consists of inorganic ions, amino acids, proteins, and organic acids. The pH of body uid is buffered at 7.15~7.35 but it decreases down to 5.2 during an inammation reaction. Macrophages secrete active oxygen species, which chemically attack the surface oxide lm of metallic materials, the inuence of the presence of macrophages has been investigated.

Macrophages secrete broblast growth factor, inducing broblasts, which produce collagen and polysaccharide for encapsulation of the implanted material. The thickness of capsular tissue depends on the biocompatibility and the size of material. With the cure of inammation, the macrophage disappears within a few weeks and the cells originating from the surrounding tissue adhere to the surface of material. These mechanical degradations are often caused by fatigue, fretting fatigue, and wear accelerated by corrosion.

Types of corrosions: useful corrosion and harmful one. Useful one that degrades when implanted to help formation of new bone that is capable of carrying the load alone instead of the implant like adding manganese alloys as WE43 and AE21 to bioadsorbable devices. Harmful one is the one that can eat in the implant and cause its decrease in volume which lead to its disfunction-ability by losing it function which have been implanted to.

Stress shielding

The reduction in bone density as a result of removal of normal stress from the bone by an implant. Wolff's law states that bone in a healthy person or animal will remodel in response to the loads it is placed under. Therefore, if the loading on a bone decreases, the bone will become less dense and weaker because there is no stimulus for continued remodeling that is required to maintain bone mass.

As we see here, the implant cares all the load by itself and the new bone that is formed doesnt carry anything. The characteristics of the metal used here in found to be of high modulus. So we use a metal with low modulus to prevent this phenomena. Comparison between different metals:

MEMS & NANOCRYSTALS

The Story:

What are MEMS/bioMEMS?

Microscopic Electro-Mechanical Systems or MEMS.

MEMS and bioMEMS are miniaturized (sub-micrometer to millimeter) systems, often produced using batch fabrication techniques.

operating principles often relies on:

! Of mechanical and fluidic components that allow physical functions to be performed in conjunction with electrical functions.

Or Vibrating

Rotating

Moving

A variety of (PVD - Physical Vapor Deposition) systems is available for depositing thin film metals relevant for MEMS fabrication. Thin metal films enter the bioMEMS fabrication flow at various crucial moments.

Ti or Cr
Cu, Au and Al

! Are commonly employed to promote adhesion between underlying layers with the new layers or structures being subsequently built atop.

! Are commonly used as electrical conductors.

Au
Cu, Au, Ni, Ni-Fe and platinum metals (Pt, Rh, Pd etc.)

! Is often used to provide a site for antibodies or single DNA strands to be immobilized. ! Are a few of the numerous materials commonly plated in a very large number of applications for their electrical, magnetic or mechanical properties.

When adequately patterned, such films can be used to produce conducting lines, electrodes, etc. Their hydrophilic or hydrophobic properties can also be used for biology applications

Plated metals may be accompanied with various levels of in-plane and out-of-plane stress.

Stress can be controlled through varying the:

Deposition rate (current density), The temperature, The agitation, The chemistry of the bath, etc.

The size of the plating cell can also inuence the reproducibility of the deposit characteristics.

Ti in Biomedical application
Ti is often used in conventional biomedical application (e.g., for hip replacements) as it fulfils basic functions such as biocompatibility, bioactivity, resistance to corrosion and/or high resistance to abrasion.

Ti brazing is a very useful conventional encapsulation technology for pacemaker leads. Unfortunately, Ti is somehow missing from the arsenal of MEMS materials with the exception of PVD thin films: no truly MEMS-friendly machining technique allows us to deposit and accurately pattern large amounts (tens to hundred of micrometers) of Ti.

Scientists are attempting to do so, using electrophoresis to deposit thick layers of titanium oxide for MEMS application.

Nanocrystalline
Over the past 2030 years there have been increasing studies on the formation of NANOCRYSTALLINE (grain size <100 nm) and amorphous (glassy) metals for various applications. Much higher yield strength, wear resistance and corrosion resistance has been shown for some pure metals formed with such fine microstructures.

Improved corrosion resistance has also been observed with nanocrystalline metals.

Nanocrystalline Production
Methods that have been reported for forming nanocrystalline and amorphous metals and coatings involve:
Rapid melt cooling rates through atomization or melt spinning methods, Extreme mechanical deformation to give heavy mechanical deformation Followed by recrystallization anneals to yield high nucleation rates with limited grain growth, Mechanical attrition or milling of gas atomized powders followed by plasma spraying (for coatings), Pulsed electrodeposition and other PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition) methods (for coatings and possibly bulk components).

In addition to developing very fine grain structures, some of these approaches also offer the possibility of unique non-equilibrium phases forming at room temperature.

The determination of the properties of the novel compositions and structures possible by these methods (including their biocompatibility characteristics) presents an exciting area for future biomaterials research.

Basamat Seif Omar AbdulRAHIM Omar Alaa Salah FathALLAH Mohamad Mehany

THANK YOU! (QUESTIONS)

Ahmad Waleed