BME/MatE 175

Biomaterials

Fall 2017

Biomaterial Requirements

Molecular Origins of Biomaterial Behavior

Instructor: Melinda Simon
Agenda

Announcement, clarifications
Results of Getting to Know You Survey
Requirements for biomaterials
Biocompatibility
Mechanical properties
Molecular Origins of Biomaterial Properties
types of chemical bonds
crystal structures
Class waitlist and add codes

There are currently 7 seats open for the class, and 10

people on the waitlist
Add codes will be given out some time this week (likely
not today)
You may not have a choice on the lab section

Meeting time Current enrollment

M 9:00 am Full
F 10:30 am 17
F 3:30 am 19
F 6:00 pm 16
Term Paper Team formation and topics
Assemble into groups of 2 within Tentative schedule
your lab section (deadline: Sept. 1) Date Topic
Deadline for group
Our TAs have created a page on the September 1
assembly
Canvas site. Once you have selected September 8 Deadline to choose topic
a partner for the project, please drag September 28 Progress Report 1
and drop both names into the same October 26 Progress Report 2
project group.
November 21 term paper final
No more than one graduate student research paper
Nov 27 - Dec 1
per project group presentations

September 4- Topics posted at Deliverables

10am on Canvas Term paper: 10 pages,
One student from each group must digital copy only
email me with your top 3 topic
Presentation: in class,
choices (first come, first served)
during lab time
September 8 Teams who have not
specified a topic will be assigned a
topic
E Textbook update

Textbook ordered on 8/23 should

arrive soon

There will be 2 copies available,

loanable for up to 2 hours at a time
iClicker Registration

55/80 students registered so far (as of 8/28 12pm)

Email or see me if you have questions on getting it set up
Students in add limbo
I will make decisions by Wednesday so that you will have time to set
up iClicker before class on Thursday
Please go ahead and create an iClicker account, so all you have to do
is link to this class once youre added

I will begin using iClicker polls on Thursday, 8/31

Lecture topics you are most interested in
This will help me make a list of project topics
Which topics have been covered well by
other courses?
Future Plans

Undecided
14%

Looking for
employment
Work, then 39%
grad school
27%

Graduate
school
18% Current
company
2%

Coffee with a Professor!

http://www.sjsu.edu/studentaffairs/about_us/chatwithaprof/
 Learning objectives

By the end of this class, you will be able to:

identify desirable biomaterial attributes from the clinician,
manufacturer, and patients perspectives
define basic concepts: biomaterial, biocompatibility
describe the three classes of biomaterials and the chemical bonds that
characterize each
identify common crystal structures and explain how these structures
relate to observed material properties

A. Bellofiore BME/MatE 175 Fall 2016

 Biomaterials

Write down 3 attributes a biomaterial should have from the point

of view of

manufacturer

clinician

patient

A. Bellofiore BME/MatE 175 Fall 2016

 Biomaterials: attributes

Manufacturer Clinician Patient

profitable easy to insurance-

manufacturable operate/deploy covered
reliable minimally invasive biocompatible
free of defects reusable durable
sterilizable low maintenance comfortable
easy to sterilize non-durable convenient
modular design insurance- quality of life
biocompatible covered effective
sustainable biocompatible
insurance-
covered

A. Bellofiore BME/MatE 175 Fall 2016

 Biocompatibility: definition

The ability of a material to perform with an appropriate

host response in a specific application.

Examples of appropriate host response:

Resistance to blood clotting
Resistance to bacterial colonization
Uncomplicated healing

Must do the patient no harm

A. Bellofiore BME/MatE 175 Fall 2016

Biocompatibility

Key Considerations:
Application
needs for implanted and non-implanted devices differ
Material
mechanical properties, susceptibility to corrosion
Processing
smooth or roughened surface desirable?
strengthening metals at the expense of increasing brittleness
Time
degradable or non-degradable?
Effect of interaction(s) locally and systemically
 Biocompatibility Testing

As a result of varying requirements,

Tests need to be application- and tissue-specific

Dominated by surface characteristics, e.g.,
roughness, porosity, charge, chemistry, surface
tension (of the solid), texture, subsurface grain
structure, wettability, etc.

A. Bellofiore BME/MatE 175 Fall 2016

 Molecular Origins of Biomaterial Behavior:
Chemical Bonds

Primary bonds (interatomic)

Covalent
Ionic
Metallic
Ionic/Covalent mixed character
Secondary bonds (interatomic/intermolecular)
Polar bonds
Nonpolar bonds

A. Bellofiore BME/MatE 175 Fall 2016

 Covalent Bonds

Electron sharing to fulfill the octet rule

Predominantly polymers and other organics
Relatively strong
Rotation of atoms is possible
carbon chain backbone
crosslinking between chains

Materials are deformable due

to the ability of bonds to rotate Source: Askeland & Phul, The Science and
Engineering of Materials, 5th Ed.

Electrons are not free chemical

inertness, nonreactivity

A. Bellofiore BME/MatE 175 Fall 2016

 Ionic Bonds
Electron transfer generates ions
Bonding is due to electrostatic attraction among ions
Predominantly found in ceramics
Very strong bonding, equal strength in all directions
Intolerant to lattice deformation (applying tension, bending)

Source: Askeland & Phul, The Science and Engineering of Materials, 5th Ed.

Materials are brittle but have a high strength and stiffness

A. Bellofiore BME/MatE 175 Fall 2016

 Metallic Bonds
Interatomic interaction
delocalizes electrons, creating
quasi-free electrons, a.k.a.
electron cloud or sea of
electrons
Predominantly found in metals
Accounts for good thermal and
electrical conductivity
Bond strength varies - generally
weaker than covalent and ionic

Nondirectional bonds easily

broken but also easily re-formed
after deformation (ductility) Source: Askeland & Phul, The Science and
Engineering of Materials, 5th Ed.

A. Bellofiore BME/MatE 175 Fall 2016

 Electronegativity
Electronegativity measures how strongly an atom holds onto its
electrons.
The nature of the chemical bond between two atoms depends
on the difference in their electronegativity.
Pauling scale

A. Bellofiore BME/MatE 175 Fall 2016 Source: Chemistry, Moore/Stanitski/Jurs, Thomson, 2006, pg 355
 Electronegativity
Atoms with comparable electronegativity equally share their
valence electrons (covalent bond).
Atoms with very different electronegativity form ionic bonds.

A. Bellofiore BME/MatE 175 Fall 2016 Source: Chemistry, Moore/Stanitski/Jurs, Thomson, 2006, pg 355
 Ceramics: covalent/ionic mixed bond

Ceramic compounds have covalent and ionic

character to their bonds

The ionic character increases with increasing

difference in electronegativity
Oxides: typically ~ 75% ionic bonding
Nitrides: typically ~ 45% ionic bonding
Carbides: typically ~ 20% ionic bonding

A. Bellofiore BME/MatE 175 Fall 2016

 Secondary bonds

A dipole is a molecule with a spatial separation between the

negative and positive charge
Permanent dipoles (polar molecules)
Fluctuating (instantaneous) dipoles
Induced dipoles
+

Secondary bonds are much weaker than primary bonds

A. Bellofiore BME/MatE 175 Fall 2016

 Secondary bonds
Types of secondary bond Introductory Chemistry CK-12, LibreTexts
https://chem.libretexts.org/Textbook_Maps/I
ntroductory_Chemistry_Textbook_Maps/
Fluctuating induced dipole bond
Permanent dipole induced dipole bond
Permanent dipole bond
Hydrogen bond

Source: Askeland & Phul, The Science and Engineering of Materials, 5th Ed.

A. Bellofiore BME/MatE 175 Fall 2016

 Bonding Energies
Material Bonding Type Bonding Energy (kJ/mol)
NaCl Ionic 640
MgO Ionic 1000
Si Covalent 450
C (diamond) Covalent 713
Hg Metallic 68
Al Metallic 324
Fe Metallic 406
W Metallic 849
Ar Van der Waals 7.7
Cl2 Van der Waals 31
Cl-Cl Covalent 242
NH3 Hydrogen 35
H2O Hydrogen 51
O-O Covalent 138
H-H Covalent 434
A. Bellofiore BME/MatE 175 Fall 2016
Crystallographic structure
Metals and alloys (e.g. Ti) can accommodate different
arrangements of atoms
Can be altered through processing to change material properties

Crystal Structure of Metals, Introductory Chemistry (CK-12)

https://chem.libretexts.org/Textbook_Maps/Introductory_Chemistry_Textbook_Maps/

Crystallographic structure affects observed mechanical properties

of material (i.e. ductility, fatigue strength, Youngs modulus)
 Crystal Structure and Microstructure

Microstructure
Distribution of grains and phases in a solid

heavily process-dependent

A. Bellofiore BME/MatE 175 Fall 2016

Surface Properties of Biomaterials
Ratner text, Ch. I.1.5

In addition to bulk mechanical properties, surface properties

govern the success of biomaterials and implants

Surface properties are different from bulk properties

Surfaces are easily contaminated (e.g. oxidation of metals)
Characterizing Surface Properties
Ratner text, Ch. I.1.5
In addition to contact angle, surfaces may be characterized by:
electron spectroscopy for chemical analysis (ESCA)
secondary ion mass spectrometry
scanning electron microscopy (SEM)
infrared spectroscopy
scanning tunneling microscopy (STM), atomic force microscopy (AFM),
scanning probe microscopy (SPM)
many others
This will be discussed in greater detail in Lab 2
Applications of Surface Characterization
Ratner text, Ch. I.1.5
Troubleshooting contamination during manufacturing
ESCA used to detect, monitor intraocular lens production for surface
contaminates
ESCA, SIMS enabled identification (and elimination) of a contaminating
fluorine source used during autoclaving of titanium implants

Predict biofouling in vivo

Determine rate of platelet deposition on polyurethanes by ESCA, and
correlate to percentage of hydrocarbon-type groups
Contact angle measurements reveal adsorption of different cell types
(bacteria, RBCs, granulocytes)
SIMS can quantify, identify some types of protein contamination on surfaces

Characterization of degradation
SIMS provides degradation information for poly(glycolic acid), an important
polymer for tissue engineering and drug delivery applications
 Surface tension: contact angle

The surface tension is directed parallel to the interface and tends

to minimize the surface energy by minimizing the interface area.
At equilibrium, the surface tensions balance each other:

sg = sl + lg cos Youngs equation

https://www.kruss.de/services/education-
theory/glossary/youngs-equation/
A. Bellofiore BME/MatE 175 Fall 2016
 Surface tension: contact angle
The contact angle is a measure of the wettability of a material.
How will a biomaterial interact with (aqueous) bodily fluids?

When in contact with water:

a material with large is hydrophobic (conventionally > 90)
a material with small is hydrophilic (conventionally < 90)

> 90 < 90
negligible wetting good wetting
hydrophobic hydrophilic

sessile drop test

A. Bellofiore BME/MatE 175 Fall 2016
 Question

According to the conventional definition, the solid surface pictured

below is classified as:

A. hydroponic

B. hydrophobic

C. hydrophilic

D. hydroplastic

A. Bellofiore BME/MatE 175 Fall 2016

 Surface tension: biocompatibility
Walter (2010)

The single biggest factor in determining BMS BMS

thrombogenicity in blood-contacting
implants is the condition of the surface.

Studies have correlated thrombogenicity DES DES

with the surface energy (or surface
tension) of biological implants.

A more wettable implant interacts more

with blood, which increases platelet before after
blood exposure blood exposure
adhesion on the implant surface.

A. Bellofiore BME/MatE 175 Fall 2016

Assignments
Reading
Agrawal Chapter 1, "Introduction" chapter, by Aug. 31

Homework 1
posted on Canvas on Sept. 7, due Sept. 14 at 10:30AM

iClicker setup
Instructions posted under Assignments on Canvas, due Aug.
30