A Cost-Effective AFM Analysis Project: Comparative Study of the

Morphology & Microstructure of Etched Zirconia & Alumina

By: Carlos Alonzo & Steve Pratt,
Eastman Kodak;
Ray Eby

Specifications
AFM Modes:
Instrument:
Digital Instruments
AutoProbe M5

Mode:
Non-Contact Topography

Accessories:
SPMLab Data Processing
Software with Grain Analysis
Option

Samples:
1.Polished & thermally etched
yttria stabilized zirconia
(ZrO2-Y2O3)
2.Polished & thermally etched
Alumina (Al2O3)

Purpose of Study
Historically, studies having to do
with the microstructure and
morphology of ceramics were
done with more conventional
microscopy techniques, namely,
polarized optical imaging or electron microscopy. Depending upon
the material grain size, either technique was considered adequate.
Now, with a significant increase in
awareness on the importance of surface structure to microstructure (and
with the consequent need for
nanoscale resolution in the z-direction) the use of Atomic Force
Microscopy (AFM) has increased in
studies that characterize ceramic
compounds. Typically, ceramic
grain size analysis and characterization required thermal etching and
coating the sample with a conductive coating or low-voltage excitation for electron microscopy. In this
case study, it was estimated that
more traditional methods of characterizing the 16 samples would
involve 8-10 days cycle time at a
cost of $11,000. But by using
the M5 AFM, cycle times were cut
to 2 days at a cost of $1,500.

Background Application Issues

Sixteen samples of various compositions of zirconia ceramics and comparative alumina ceramics were
examined with the AFM. The samples were each polished and then
thermally etched in order to
enhance the microstructure and
grain textures. The microstructural
properties of interest are grain size,
grain boundary depth and general
grain morphology. Using electron
microscopy to see the grain
microstructure would require examining only a few grains at time at
very high magnifications, resulting
in a low statistical sampling rate.
Conversely, the AFM can image
many more grains at a time and
provide superior resolution of the
individual grain textures.

Figure 1. Zirconia Sample #1 - Polished & etched, scanned with AFM; 8mm and 4mm scan sizes

Results
Images of two zirconia samples are
shown in Figures 1 & 2. First, the
general appearance of the two
zirconia samples is quite similar.
Grain shapes do not differ between
samples, and neither does the grain
boundary texture. The surface
roughness values after polishing
and etching are essentially identical
(rms #1 = 16.7 nm; #2 =
16.4 nm). Two subtle differences in
these zirconia samples are: (i) a
larger grain size observed in
Sample #2; and (ii) the slightly
more complex surface texture of
grains in Sample #1, as observed
in the 4 mm scans. Grains in sample #1 appear to have a more serrated surface texture.

Figure 2. Zirconia Sample #2 - Polished & etched, scanned with AFM; 15mm and 4mm scan sizes.

Figure 3. Alumina Sample - Polished & etched, scanned with AFM; 9mm and 4.5mm scan sizes

Images of the comparative alumina

sample are in Figure 3. Clearly, there
are substantial differences seen from
the zirconia samples. The average
grain size in the zirconia is about
twice that of the alumina and the
grain boundaries have much deeper
pits that developed at the triple-point
boundaries. The surface texture of the
alumina grains is highly serrated as a
result of the thermal etching process.
This kind of texture is commonly
observed in industrial alumina films
which have undergone thermal treatment, most notably as used in the
integrated circuits industry.
Results of grain analyses on the zirconia samples are shown in Figures 4
and 5. Figure 4 shows an image
before and after several filtering functions were applied. The unfiltered
image is unshaded and thus looks different from Fig. 1, but it is not.
Sharpening, Laplacian and smoothing filters all served to substantially
enhance the grain boundaries at the
expense of the surface texture on the
grains, which in turn allows the grain
analysis routine to better define the
grain boundaries. Figure 5 shows the
grain analysis output from Sample #2
in which the grain boundaries are
reasonably well defined. Table 1 lists
some of the statistical differences
between the two zirconia samples.

Table 1:

Statistical Analysis of Grain Size Characterization

Sample #

Average Area (mm2)

Mode of Area (mm2)

Std Dev of Area (mm2)

0.11

0.11

0.08

0.21

0.12

0.26

Figure 4. Zirconia Sample #1 - Before (left) and After (right) image processing filters were applied.

Although the modal grain size distribution is very similar for the two samples (i.e., the histogram peaks have
a similar position), the average grain
size is substantially different. The difference is a result of the presence of
a small fraction of much larger grains
in Sample #2.
Figure 5. Zirconia Sample #2 - Example Output from Grain Analysis Routine of SPMLab Software.
(more defined bimodal grain size distribution in Sample #2

Discussion on Sub-grain texture

and features

References
[1] Based on atomic radii values. J. Emsley, "The Elements."
2nd Ed. Oxford 1991.

The serrated texture found in the alumina is believed to be the product

of dislocations, slip lines or stacking
faults (sub-grain defects). These
material features have been hidden
from typical grain size analysis in
the past due to the limited resolution
of optical microscopy and SEM
techniques. Historically, these features could only be detected using
Transmission Electron Microscopy
(TEM).
The AFM used in this study has an
Angstrom-scale resolution limit. A
zirconia molecule is estimated to
have a diameter of 5 , which
means that, theoretically, any dislocation, slip line or stacking fault on
the surface of the zirconia samples
will be detected by AFM. Further
analysis would have to be performed to prove the observation of
these sub-grain features by AFM
and would most likely have to cross
reference to electron microscopy. It
is possible that after further analysis,
AFM could become an alternative
tool to TEM in the study sub-grain
defects.

Conclusion
M5 AFM was used to efficiently
characterize ceramics, and powerful software has further supported
this effort.

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