Current Techniques in Failure Analysis

by
Dwight G. Weldon
Weldon Laboratories

Causes of Failure

Bad application
Defective coating
Inappropriate specification
Unanticipated environmental excursion

Begin at the microscope

Many coating failures are due to simple things,
such as the paint being too thick or too thin, or
applied over dirt.
A stereo microscope with magnification up to 3040X is invaluable. If it doesnt solve the problem,
it may at least give clues as to what may have
happened.
Some time at the microscope might save many
hours of expensive laboratory work.

Dry-sprayed zinc-rich

Too much aggregate

Zinc primer insufficient profile

Analytical Techniques
Or, when the microscope isnt
enough!

Some common analytical

techniques include:
Infrared Spectroscopy
Gas Chromatography (GC and/or GCMS)
Scanning Electron Microscopy Energy
Dispersive X-ray Spectroscopy (SEMEDS)

Infrared Spectroscopy
Identifies a sample based on its absorption
of infrared light at various frequencies.
An extremely useful tool. It is often the
technique of choice following the
microscopic observations.

Infrared Spectroscopy-How it works

The molecules making up a sample are in a
constant state of motion, and vibrate at various
frequencies.
These frequencies depend on the type of atoms,
and the type of chemical bonds holding them
together. For example, a hydrogen atom singlebonded to a carbon atom will have a stretching
vibration near 2900 cm-1, and an oxygen atom
double bonded to a carbon atom will have a
vibration in the 1650-1750 cm-1 region.

Example of Infrared Vibrational

Modes

Infrared Spectroscopy - How it works

Continued
The frequency of light which corresponds
to these molecular vibrations occurs in the
infrared region of the electromagnetic
spectrum.
When infrared light is focused on or
through a sample, the sample will absorb
those frequencies of light which match the
frequencies of its internal molecular
vibrations. This results in a spectrum.

Infrared Spectroscopy - How it works

Continued
The infrared spectrum is highly
characteristic of the type of molecules
making up the sample. Because different
molecules have their own, unique infrared
spectrum, the spectrum is sometimes
referred to as a fingerprint.

Uses of Infrared Spectroscopy

Identification of coating type
Identification of some pigments
Determination of degree of cure for some
coating types (inorganic zinc-rich primer,
urethanes, possibly others).
Determination of mix ratio for multi-component
coatings
Contamination
Blushes/exudates
Batching variations

IR spectra of generic coating types

Degree of cure of urethane

Mix ratio of epoxy coating

Limitations of Infrared
Spectroscopy
Usually qualitative, not quantitative.
Limited information on inorganic materials.
Cannot identify minor (<5%) ingredients in
a complex mixture.
Bands can be broad and overlapping ( a
paint can have many ingredients),
obscuring important information.
No information on molecular weight.

Gas Chromatography (GC)

Analyzes volatile and semi-volatile
materials by using a gas to flush them
through a special column at an elevated
temperature. A fancy, expensive oven.

GC: How it works

The column is kept at an elevated temperature,
with a flow of gas (typically helium) running
through it. The end of the column is connected
to a sensitive detector.
A syringe is used to inject a small amount of
sample (either a liquid or a gas) into the column.
Since the components of interest are volatile or
semi-volatile (solvents and monomers), their
vapors will be swept through the column by the
helium carrier gas.

GC: How it works

Continued
The inside of the column is either packed with or
lined with a stationary phase. One common type
is a high-boiling modified silicone.
Different solvents will have either a greater or a
lesser attraction to the stationary phase inside
the column. Those which have the least
attraction will go through the column the fastest.
When the different solvents pass through the
column they will be detected by the detector,
resulting in a series of peaks eluting at different
times. This is called a chromatogram.

GC: How it works

Continued
The solvents can be identified (sometimes
with difficulty) by the time in which it took
them to exit the column (retention time), or
by using a mass spectrometer as a
detector (GC-MS).
The height or area of a peak is
proportional to the amount of that
particular solvent, allowing quantitative
analysis to also be performed.

GC

Example of gas chromatogram

Uses of Gas Chromatography

Detect and identify solvents and
monomers at ppm (sometimes ppb) levels.
Detect residual amounts of solvents in dry
paint chips (via solvent extraction or
analysis).
Analyze the liquid trapped inside blistered
paint for solvents.

Limitations of Gas Chromatography

Compounds must be volatile or semivolatile.
Dry paint chips for residual solvent
analysis should not be too old.
Identification of unknowns based solely on
retention time can sometimes be difficult.
This problem can be overcome with a
mass spectroscopy detector.

Scanning Electron Microscopy Energy

Dispersive X-ray Spectroscopy (SEM-EDS)

An SEM provides high magnification

(1000X and above) images with good
depth of field. It allows one to see features
not observable with a stereo zoom
microscope.
When interfaced with an EDS detector, the
elemental composition of very small
objects can be determined.

SEM image of a zinc-rich primer

SEM image of crystal growth inside

a coating void due to permeation of
tank contents

SEM-EDS: How it works

An electron gun, typically consisting of a
tungsten filament and associated apparatus,
produces a beam of high energy electrons.
Electromagnetic lenses are used to focus this
beam of electrons on a small sample mounted in
an evacuated chamber.
The collision of electrons with the surface of the
sample creates scattered electrons, which are
collected and result in the magnified image.

SEM-EDS: How it works

Continued
When the beam of energetic electrons collides with the
atoms making up the sample, in addition to producing
scattered electrons for imaging, x-rays are also
generated.
Different chemical elements produce x-rays of differing
energies, which allows the elements to be identified.
Elements can be rapidly and simultaneously detected.
Normal detectors can detect any element of atomic
number 11 (sodium) and higher. Light element detectors
can go down to atomic number 6 (carbon).

Example of SEM-EDS spectrum

Applications of SEM-EDS
The examination of samples at several hundred
times magnification and higher allows one to see
inclusions, residues, phase separations, etc.
Not only can the elemental composition of the
sample be determined, but the composition of
inclusions, residues, and other small particles
can be determined as well.
Determine the composition of a failing surface
(identifying the failure plane).
Detecting salts or other contaminants in
corrosion products.

Limitations of SEM-EDS
Identifies elements, not compounds.
Very limited ability to detect organic
compounds.
Relatively poor detection limits (about
0.1%).
Elemental analysis is only semiquantitative.

Solving Failures
Sometimes coatings fail for very simple
reasons; sometimes they fail for very
complicated or subtle reasons.
However, with good background
information and proper samples, most
coating failures can be solved.