You are on page 1of 5

2014-09-04

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


materials:

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

2014-09-04

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

Physical

Chemical Analysis

Contact Angle

Electron Spectroscopy, Light Spectroscopy (FTIR, NMR,


Raman), Mass spectrometry

Microscopy

Light, Electron, Scanning Probe

2014-09-04

Contact Angle

Contact Anglebalance
between molecular
cohesive and adhesive
forces

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

Spectroscopy

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
atoms

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

Spectroscopy

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
required

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

2014-09-04

Scanning Probe Microscopy: AFM

Atomic Force Microscopy

Tip deflection measured

Tip Interaction modes

Hookes Law

Can probe down to atomic


level
Topographical
Contact, Lateral force,
Non-contact, Tapping,
Phase shift (mechanical
properties)

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
surface

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


denaturation
Right sidechaotropes, increase protein solubility, increase
denaturation

Surfaces alter water structure and entropy drives the


stability of many interactions

2014-09-04

Surfaces vs. Bulk

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


surrounding environment sees the surface of a material

Interfacial/Surface
Energy

Surface molecules rearrange themselves (if possible) to


minimize impact of being exposed to environment

Modification of
Surface

Patterning/geometry/topography, surface chemistry, porosity,


depth of surface zone, crystalline vs. amorphous

Physical Surface
Analysis

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


Electron

Examine morphology of material at a micro and nano level

Microscopy: Scanning
Probe

AFM: measure deflection due to topography or force, very


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

Water

Hydrogen bonds, less dense when solid, high heat capacity