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Learning Objectives

After the Surface Properties lecture and assignment, you

should be able to:

Differentiate between bulk and surface properties

Correctly categorize several properties as being bulk or

surface properties

Discuss the importance of understanding a materials surface

Describe 3 techniques used to analyze surface properties,
highlighting similarities/differences

Surface Properties

To properly design devices, we need to understand a


Physical Properties (mostly bulk)

Durability (bulk and surface)

Biocompatibility (surface)

The surface of a biomaterial is all that the environment

sees and therefore dictates the biological response

Special reactivity due to loss of continuity present within bulk

Surface Bulk

Surfaces are most often contaminated

Surface molecules have high mobility


Surface Properties

Definition: Surface is the zone within which properties vary

compared to the bulk

Interfacial Energy minimization drives the process of

molecular rearrangement at the material surface

Surface Analysis


Chemical Analysis

Contact Angle

Electron Spectroscopy, Light Spectroscopy (FTIR, NMR,

Raman), Mass spectrometry


Light, Electron, Scanning Probe


Contact Angle

Contact Anglebalance
between molecular
cohesive and adhesive

Force balance between

surface tension and
interfacial tension

Measured as the angle

of interaction between
a liquid and solid.

Surface Energy:

sv = sl + lv cos


Fourier Transform Infrared Spectroscopy

(FTIR)absorption of light due to
vibrational molecular motion

Challenges: sensitivity, only analyzing

surface not bulk

Nuclear Magnetic Resonance probes

quantum mechanical magnetic properties of

1-5 m depth of analysis down to 10 nm

depth depending on method

Challenges: not overtly surface-focused,

only applicable in certain circumstances

Raman spectroscopyinelastic scattering of

light due to vibrational molecular motion

Same challenges as FTIR


Electron Spectroscopy for Chemical Analysis (aka X-ray

photoelectron spec XPS)

Binding Energyatomic electrons = hvx-ray Kinetic Energyemitted electrons

Advantages: no sample prep, 8-10 nm depth, lots of info, speed

Challenges: high vacuum, sample damage, cost and expertise

Secondary Ion Mass Spectrometry

Accelerate ions towards surface

Sample emits secondary ions, analyze the mass to charge ratio
Static: 1-2 nm depth; dynamic: can erode the sample surface to
check depth profile
Same challenges as ESCA


Scanning Probe Microscopy: AFM

Atomic Force Microscopy

Tip deflection measured

Tip Interaction modes

Hookes Law

Can probe down to atomic

Contact, Lateral force,
Non-contact, Tapping,
Phase shift (mechanical

Artifacts problematic,
extremely sensitive to
contamination, typically
under vacuum

Scanning Probe Microscopy: STM

Electron cloud of metal tip

terminating in 1 atom interacts
with electron cloud of sample

Applied potential creates

electron tunneling current J
between tip and surface
( Ak0 S )

A is a constant, k0 is avg.
inverse decay length (related to
electron affinity), S is
separation distance

Monitors electron density

J e

Water is Awesome

Dissolved ions perturb the surrounding water structure

Hofmeister series of anions:

CO32- > SO42- > S2O32- > H2PO4- > F- > Cl- > Br- > NO3- > I- > ClO4-> SCN

Left sidekosmotropes, precipitate proteins, inhibit

Right sidechaotropes, increase protein solubility, increase

Surfaces alter water structure and entropy drives the

stability of many interactions


Surfaces vs. Bulk

Surface is (by definition) different from the bulk; the

surrounding environment sees the surface of a material


Surface molecules rearrange themselves (if possible) to

minimize impact of being exposed to environment

Modification of

Patterning/geometry/topography, surface chemistry, porosity,

depth of surface zone, crystalline vs. amorphous

Physical Surface

Contact angle tells us about cohesive and adhesive forces,

measured as angle of interaction between liquid and solid

Chemical Surface
ESCA / XPS; X-rays eject characteristic electrons from material;
Analysis: Electron Spec 8-10 nm depth; high cost, damage, and vacuum
Chemical Surface
Analysis: Light Spec

FTIR and Raman: absorption of light resonant with vibrational

molecular motion; 1-5 m depth; sensitivity low

Chemical Surface
Analysis: Mass Spec

Secondary ion mass spectrometry; Accelerated ions eject 2o ions

from material (analyze mass/charge ratio); 1-2 nm depth; high
cost, damage, vacuum

Microscopy: Light and


Examine morphology of material at a micro and nano level

Microscopy: Scanning

AFM: measure deflection due to topography or force, very

sensitive technique; STM: electron cloud tunneling current
measures electron density of material


Hydrogen bonds, less dense when solid, high heat capacity