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Biomaterials - I

BME 379/385, CHE 379, Spring 2003 (Schmidt)

Goals:
By the end of this lecture, you should be able to:
• Describe the key pros/cons of different materials
• Describe different mechanical tests & interpret data
• Describe differences between metals, ceramics, polymers
• Identify condensation & addition polymerization reactions
• Define thermoset & thermoplastic polymers
• Calculate average molecular weight of a polymer
• Calculate degree of polymerization for a polymer
• Discuss the properties that affect polymer degradation
• Describe different polymers processing techniques

Outline:
I. Introduction & General Classification of Materials
II. Analysis of Material Properties
III. Polymer Basics
A. Classification
B. Polymerization Reactions
C. Copolymers
IV. Polymer Properties
A. Desired Polymer Properties
B. Thermoset & Thermoplastic Behavior
C. Elastomer Behavior
D. Hydrogels
V. Polymer Degradation & Biodegradable Polymers
VI. Polymers Processing for Tissue Engineering
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I. Introduction & General Classification of Materials


Define "biomaterial":

List key pros/cons & common biomedical uses of current materials:


• Metals

• Ceramics

• Polymers

• Composites
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Metals:

Titanium

Gold

Ceramics:

Hydroxy apatite

Pyrolytic carbon
LTI pyrolytic carbon
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Polymers:
Natural polymers

Synthetic polymers (non-degradable)


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Synthetic polymers (degradable)

II. Analysis of Material Properties


Biomechanics
Failure analyses (tensile fracture, compression, shear stress,
fatigue, wear,...)

Structure & Geometry


Imaging techniques (photography, microCT, histology)
(not discussed in class)

Biocompatibility and Cell Response


(discussed in later lectures)
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Biomechanics
A common property measured of most materials is tensile strength:

2 3
B
1
Stress A

Strain
To construct this tensile stress-strain plot, a rod or "dog-bone"
shaped material specimen is stretched using a mechanical test
machine (instron). Force (Newtons) is applied to the specimen, and
deformation of the specimen is measured (mm). Stress, σ (N/m2 or
Pascals), is calculated as force divided by the original cross-sectional
area. Strain, ε (%), is calculated as the change in length divided by
the original length.

For the plot above:


Region A =
Region B =
Point 1 =
Point 2 =
Point 3 =
Young's modulus (E) or stiffness =
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Example Problem: You are to design a cable that must support an elevator cab that
weighs 10,000 lb. The cable is made from the aluminum alloy, whose data is presented in
the figure below. Calculate the minimum diameter of the cable required to support the
cab without permanent deformation.

Expanded View
Stress-Strain for Alluminum Alloy
40000
45,000
35000
40,000

35,000 30000

30,000 25000

Stress (psi)
Stress (psi)

25,000
20000
20,000
15000
15,000
10000
10,000

5,000 5000

0 0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0 0.001 0.002 0.003 0.004
Strain (in/in) Strain (in/in)

Stress-strain curves can also provide information on brittleness vs.


ductility….

Stress

Strain

Which curve above represents the behavior for a brittle material?

A ductile material?
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Other biomechanical tests:


Compression

Fatigue Wear
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III. Polymer Basics


Polymers can be defined as:

Polymer advantages over metals and ceramics:


1.
2.
3.
4.
5.

Polymer disadvantages compared to metals and ceramics:


1.
2.

Why are polymers typically used in Tissue Engineering applications?


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A. Classification

Polymers can be classified according to:

1. Polymerization mechanism
Condensation polymerization
Addition (free radical) polymerization

2. Polymer structure
Linear
A' (A)X-2 A"

Branched
A' (A)n Y (A)n Y

(A)n (A)n

Crosslinked (networks)

3. Polymer behavior
Thermoplastic –

Thermosetting –
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B. Polymerization Reactions
1. Condensation Polymerization
R-NH2 + R'COOH --> R'CONHR + H20
(amine) (carboxylic acid) (amide)

Most natural polymers (polysaccharides, proteins) are made by condensation


polymerization

2. Addition (Free Radical) Polymerization


H H H H H H
C C C C C C
H H H H H
nH
The breaking of a double bond usually occurs using an initiator (e.g.,
free radical such as benzoyl peroxide).

The free radicals (R•) can react with monomers:


H
R• + CH2 =CHX ----> RCH2 C•
X

This free radical can then react with another monomer in a process
called propagation:
R• + M --> RM•
RM• + M --> RMM•

The propagation process can be terminated by combining two free


radicals or by transfer.
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Common condensation and free radical polymers:

Degree of polymerization (DP):

DP related to molecular weight: M w = (DP) x (M.W. of mer)

Polydispersity:
M w ∑ (Wi • MWi)/∑ Wi
=
M n ∑ (Xi• MWi)/∑ Xi

EXAMPLE: Calculate the degree of polymerization if polyethylene


(C2H4)n has a molecular weight of 100,000 g/gmol.
(How will this change for a condensation polymer?)
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Molecular weight affects polymer properties:

C. Copolymers

Definition:

Types of copolymers:
--AABBABAABBBABAABAAABBABA—

--ABABABABABABABABABABABAB—

--AAAAAA--BBBBBB--AAAAAA--BBBBBB—

--AAAAAA--AAAAAA--AAAAAA--
B B B
B B B
B B B
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IV. Polymer Properties


A. Desired Polymer Properties
Some of the properties that should be considered for the selection of
a polymer for a particular biomedical use are:
(this is what the medical doctor and engineer would specify)

The macroscopic properties of the biomaterial (above) will depend on


the following fundamental characteristics of the polymer:
(this is what the polymer chemist would control)
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B. Thermoset & Thermoplastic Behavior

Examples of plastics (thermoplastic and thermoset) and elastomers:

Thermoplastics, elastomers & hydrogels (not shown above) are most


important in BME. See handout on hydrogels.
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Thermoplastic Behavior:

How does MW of a thermo-


plastic polymer affects its
strength & thermal stability?

What are some properties and processing conditions that affect


crystallinity?
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C. Elastomer Behavior

Elastomers are highly elastic over a range of temperatures. What


provides this elastic property?

Are these materials amorphous or crystalline?

What happens at temperatures above Tm? Does the polymer liquefy?


Why or why not?

D. Hydrogels

Hydrogels are a unique form of polymers for implantation.

Definition:

Hydrogels can be up to 90% water (by weight).


Examples: agarose gels, gelatin, collagen gels, ...

Pros and Cons:

Example = contact lenses


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V. Polymer Degradation & Biodegradable Polymers


Definition:

Biodegradable polymers are also referred to as:

Biodegradable polymers are used as scaffolds for tissue engineering


applications for many reasons:

Degradation occurs via hydrolysis, enzymatic action, .

Possible concerns with degradable polymers (with respect to Tissue


Engineering):
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Common Biodegradable Synthetic Polymers:

There are several biodegradable polymers that already exist and that
are being developed for tissue engineering applications. Two of the
more common biodegradable polymers are PGA and PLA. These
materials are commercially available and are already FDA-approved
for surgical procedures (e.g., biodegradable sutures).

Polyesters:
Polyglycolic Acid (PGA)
H O H O
O C C O C C O
H H

Polylactic Acid (PLA)


CH3 O CH3 O
O C C O C C O
H H

Which polymer is likely more crystalline? Why?

What properties of the above polymers will affect degradation rates?

One can tailor polymer properties (degradation rate) by making


copolymers of PGA & PLA --> PLGA or poly(lactic-co-glycolic
acid).

Polyesters commonly used as suture material, adhesives, and in TE


applications (breakdown products are natural).
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Degradation of Biodegradable Polymers:

Factors that will affect degradation:


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Degradation (Hydrolysis) of PLGA:

These degradation products, although natural to the body, are acidic -- too fast
of a degradation rate can be detrimental to cells (pH ).

PLGA tends to degrade by bulk degradation. More hydrophobic polymers,


such as polyanhydride, tend to degrade by surface erosion.
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VI. Poymers Processing for Tissue Engineering


Polymer Foams (solvent casting & particulate leaching)

Fiber extrusion and fiber bonding


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Larger device extrusion (e.g., conduits)

Phase separation

Solid Freeform Fabrication (SFF) and 3-D Printing


(see article by Griffith; below is new development by Chen at UT)

Laser
XYZ CAD
Controller Station
Beam
Shutter

Lens

Platform

Liquid Polymer and


Container
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Simpler Methods for 3-D Polymer Processing

Chemical/Biomolecule Modification