Methodsfor Preparation of Cross-Sectional Scanning

Electron Microscopy Specimens and Their Application

to Corroded Specimens of a Zirconium Alloy and TiN
Coated Stainless Steel
Yuquan Ding and Derek O. Northwood
Engineering Materials Group, University of Windsor, Windsor, Ontario, Canada N9B 3P4

Two techniques for the preparation of cross-sectional scanning electron microscopy spec-
imens are described. The method that utilizes a tapered cross section is emphasized. This
method was developed for the examination of the oxide-metal interface in zirconium
alloy corrosion specimens. Typical micrographs are presented for the oxide-metal inter-
face in Zr-2.5wt.%Nb alloy corrosion specimens and for the TiN-substrate interface for
TiN coated stainless steel.

INTRODUCTION SEM cross-sectional metallographic sam-

The scanning electron microscope (SEM)
and the electron microprobe are two pow-
erful instruments that permit the obser-
vation and characterization of heteroge-
neous organic and inorganic materials and
surfaces on a local scale. SEM is one of the
most versatile instruments available for the
examination and analysis of the micro-
structural characteristics of solid objects,
with the advantage that many specimens
can be examined with virtually no need for
specimen preparation. Specimen thickness
is also not a major consideration as it is
when using the transmission electron mi-
croscope (TEM).
Specimen preparation does, however,
become an important consideration under
certain circumstances. For example, to un-
derstand better the corrosion and hydrid-
ing behavior of zirconium and its alloys, it
is important to obtain information on the
nature of the oxide film, particularly that
which is at or near the oxide-metal inter-
face. A number of methods for preparing
ples of coatings on a substrate, or surface
oxides formed during corrosion, has been
developed (see, e.g., refs. 1-4), but there
are relatively few reports of studies on the
oxide near the oxide-metal interface in zir-
conium and its alloys [5-9]. It is often dif-
ficult to reveal the "true" microstructure of
the oxide-metal interface formed during
oxidation of zirconium and its alloys using
the common cross-sectional methods, be-
cause the actual cross-sectioning can cause
distortion, or destruction, of the interface.
TEM examination of the oxide-metal in-
terface produces structural information
from a very much smaller area than is pos-
sible with SEM [10], and, thus, its (i.e.,
TEM) application to the study of oxidation
phenomena is more limited.
In the present work, we have devek)ped
SEM specimen preparation techniques and
applied them to the study of the oxide-
metal interface in corroded specimens of a
Zr-2.5wt.%Nb alloy (hereafter referred to
as Zr-2.5Nb) and to the coating-substrate
interface in TiN coated stainless steel.

25
©Elsevier Science Publishing Co., Inc., 1992 MATERIALS CHARACTERIZATION 29:25 33 (1992)
655 A v e n u e of the Americas, New York, NY 10010 1044 5803/92/$5.00
26
These specimen preparation techniques
should find application in other situations
where there is an interest in characterizing
the oxide-metal or coating-substrate
interface.
EXPERIMENTAL DETAILS
MATERIALS USED IN THE DEVELOPMENT
OF PREPARATION METHODS
Corroded Specimens of Zr-2.5Nb
Pressure Tubing
The starting material, i.e., precorrosion,
was commercial grade Zr-2.5Nb pressure
tubing. The chemical analysis and com-
plete fabrication details for this tubing can
be found in ref. 11. Sections of approxi-
mately 20 mm x 10 mm by the thickness
of the tubing (4 mm) were cut from the
pressure tubing using a low-speed dia-
mond saw, ground to remove the protec-
tive autoclave oxide film present in as-re-
ceived pressure tubing and cleaned using
deionized water and alcohol. Corrosion
tests were performed in high-pressure
(8.65 MPa), high-temperature (300°C)
static autoclaves containing aqueous LiOH
solutions (4.8 g LiOH/1 L deionized water).
Full details of the corrosion test procedures
can be found in ref. 11. The specimens
used in the present study were removed
from the autoclaves after 40 and 500 h
exposure.
TiN Coated Layer Stainless Steel
TiN coatings were deposited on stainless
steels by sputter ion plating. A sputtering
system was used to produce the TiN mul-
tilayer structure. Titanium with a purity of
better than 99.95% was sputtered from a
target in a mixture of argon and nitrogen.
Prior to all depositions, the chamber was
evacuated to a pressure of better than 2.7
x 10 4 Pa, and during deposition the total
pressure was kept at 0.65 Pa. The stainless-
steel substrates were in the form of strip.
The deposition temperature can be ad-
justed from 250°C to 900°C.
Y. Ding and D. 0. Northwood
SEM SPECIMEN
PREPARATION TECHNIQUES
Method 1: Tapered Cross Section
The first step in the SEM specimen prepa-
ration technique is to cut off 0.5-mm-thick
sections that contain the thin oxide layer
or the TiN coating layer. This is done using
a low speed diamond saw. These 0.5-mm-
thick sections are then glued with the oxide
or the TiN coating side down, onto short
lengths of 12.7-mm-diameter metal rods
using a thermoplastic cement (Lakeside 70,
supplied by Buehler Ltd., Lake Bluff, Ill.
USA). As well as securing the specimens
during the preparation stages, the metal
rods act as specimen holders for subse-
quent SEM examination. Aluminum rod
was used in the present study but any
nonmagnetic metal or alloy would be
satisfactory. This operation is illustrated
schematically in Fig. l(a). The metal- or
substrate-side of the specimens is mechan-
Specimen
~Thermoplastic Cement
Cement~ Metal
~ Ox
d
ie
Metal Holder l PorBl~g
o._,
MetalHolder
Co)
FIG. 1. Schematic showing the preparation sequence
for SEM specimens containing the oxide-metal
interface.
SEM Cross-Sectional Specimen Preparation 27

ically polished by hand until the under-

lying oxide or the TiN coating appears (see
Fig. l(b). Note that the polishing is done
"at an angle" so that a tapered section is
produced going from metal, to oxide-
metal interface or TiN-substrate interface,
to the outer oxide or TiN coating layer. Be-
cause the oxide layer is softer, and the thin
TiN coating layer is more friable than the
metal substrate, the oxide near the oxide/
metal interface, or the thin TiN coating
layer, is degraded during this mechanical
polishing operation. This is shown in Fig.
2(a, b), which is a scanning electron mi-
crograph of the oxide-metal interface on
one Zr-2.5Nb specimen after mechanical
polishing but before etching.
In order that the structure at and near
the oxide-metal (or TiN-substrate) inter-
face can be better revealed, the mechani-
(a)
FIG. 3. Light micrograph of the oxide-metal interface
after mechanical and chemical polishing (etching)
(same specimen as Fig. 2).
cally polished specimen was chemically
polished (etched) using a swabbing tech-
nique. A solution of 45 parts HNO3:45
p a r t s H20 : 10 parts HF is used for the Zr-
2.5Nb alloy, and a solution of 5 parts bro-
mine:95 parts methanol is used for the
stainless-steel substrate. The choice of an
appropriate etching solution is dependent
on the nature of the substrate material.
These chemically polished (etched) speci-
mens were first examined using fairly low
power light microscopy (see Fig. 3). Before
the specimens could be examined in the
SEM they were coated with a thin layer
(20-30 nm) of carbon using a vacuum dep-
osition technique. This carbon layer pre-
vents charge buildup and image degra-
dation during SEM viewing. Figures 4 and

(b)
FtG. 2. (a) Scanning electron micrograph of the oxide-
metal interface in Zr-2.5Nb after mechanical polish-
ing but before etching; (b) higher magnification mi-
crograph of area marked A in a.
FIG. 4. The oxide-metal interface in a Zr 2.5Nb spec-
imen with the oxide layer perpendicular to axial di-
rection of pressure tubing.
28 Y. Ding and D. 0. Northwood

The next two steps are mechanical pol-

ishing and chemical polishing. The me-
chanically polished specimens are chemi-
cally polished (etched) using a swabbing
technique. For the TiN coatings, a bro-
m i n e - m e t h a n o l solution is first used, fol-
lowed by another swabbing operation with
a solution of 20 parts HNO3:20 parts
CHBCOOH:I part HF. The first solution
more clearly reveals the TiN-substrate in-
terface, whereas the second solution aids
in revealing the microstructure of the TiN
(a) coating. Figure 7 is a typical scanning elec-
tron micrograph from a coated specimen
prepared using Method 2. Two distinct
TiN layers are clearly visible. The various
layers were identified by energy dispersive
spectroscopy techniques.

E0o
Method 1 is particularly suited for ob-

Til~

I Holder
Surface of TiN

(h)
FIG. 5. (a) Scanning electron micrograph of the TiN-
substrate interface in TiN coated stainless steel (SEM
specimen prepared using Method 1); (b) schematicof
structures in a. Substrate Substrate

5 are typical scanning electron micro- Ca)

graphs of either the oxide-metal or the
TiN-substrate interfaces obtained using
specimens prepared using Method 1.

Method 2
The first step in M e t h o d 2 was the same as
that for m e t h o d 1, i.e., low speed d i a m o n d
saw cutting of 0.5-mm-thick sections con-
taining TiN or oxide layer. These 0.5-mm-
thick sections are t h e n glued onto metal
rods so that the oxide or coating layer sur-
face is perpendicular to metal surface as
s h o w n in Fig. 6(a, b). To protect the oxide FIG. 6. (a) Schematic of preparation of SEM speci-
mens containing the TiN-substrate interface for SEM
or the coating during mechanical polish- examination; (b) Scanning electron micrograph of a
ing, the oxide or coating surfaces are specimen containing the TiN-substrate interface
placed facing each other (see Fig. 6(a)). (SEM specimen prepared using Method 2).
SEM Cross-Sectional Specimen Preparation 29

r o u n d i n g the c~-Zr grains (black p h a s e in

the scanning electron micrograph). The ~-
Zr grain b o u n d a r i e s are not readily visible
on the scanning electron m i c r o g r a p h but
for the section s h o w n in Fig. 8(a), the ~x-Zr
grains h a v e a thickness of 0.5-1.0 Ixm and
a w i d t h that is 10-15 times the thickness.

FIG. 7. Scanning electron micrograph of a specimen

with two layers of TiN prepared using Method 2.

servation of the microstructure at or near

the interface, w h e r e a s M e t h o d 2 can be
u s e d to o b s e r v e the microstructure of the
oxide or the coating all the w a y f r o m the
interface to the coating/oxide surface.

RESULTS FROM APPLICATION OF

SPECIMEN PREPARATION METHODS

This section of the article does not a t t e m p t

to describe in detail the nature of the oxide
barrier layer or the TiN coating, but rather
to d o c u m e n t s o m e of the m o r e i m p o r t a n t
o b s e r v a t i o n s on the oxide barrier layer and
the TiN coatings obtained u s i n g the SEM
s p e c i m e n p r e p a r a t i o n techniques that we
h a v e d e v e l o p e d , which are described in
this article. These s p e c i m e n p r e p a r a t i o n
m e t h o d s w o u l d h a v e potential application
to other materials containing an o x i d e -
metal interface or coating.

The Oxide-Metal Interface Formed

During the Aqueous Corrosion
of a Zr-2.5Nb Alloy
Figure 8(a) is a scanning electron micro-
g r a p h of an u n c o r r o d e d Z r - 2 . S N b pres-
sure tube s p e c i m e n . The microstructure
consists of filaments of a [3-Zr p h a s e (white
in the s c a n n i n g electron m i c r o g r a p h ) sur-
Fro. 8. (a) Scanning electron micrograph of uncor-
roded Zr-2.5Nb specimen (metal surface perpendic-
ular to axial direction of pressure tubing); (b) topog-
raphy of the oxide-metal interface; and (c) the oxide
formed at grain boundaries in pretransition {short
time corrosion) specimens (oxide layer perpendicular
to axial direction of pressure tubing).
30 Y. Ding and D. 0. Northwood

The o~-Zr grains in this cold-worked ma-

terial are, in fact, pancake-shaped with a
length [not shown in the section in Fig.
8(a)] that is approximately 50 times the
thickness. Transmissions electron micro-
graphs of this material show that these e~-
Zr grains contain subgrains and have a
high dislocation density [11]. Comparison
of this micrograph with micrographs from
tapered sections of corroded specimens
[Fig. 8(b, c)] illustrates very well the rela-
tionship between the underlying metal
structure and the oxidation process. In
these micrographs the oxide layers are per-
pendicular to the axial direction, i.e., we
are looking at a radial-circumferential sec-
tion. Oxidation of the cold-worked Z r -
2.5Nb pressure tubing in pressurized lith-
iated water proceeds mainly along grain
boundaries at which filaments of the [3-Zr
phases are present (inferred from the fact
that the geometrical distribution of oxide
is similar to that of the eL-Zr grain bound-
aries). Figure 8(b) indicates that there is a
definite demarcation line between oxide
and metal at the interface in pretransition FIG. 9. Topography of the oxide-metal interface (a)
specimens, i.e., in specimens exposed for and the oxide (b) formed at grain boundaries in post-
transition (long time corrosion) specimens (oxide
short times prior to "breakaway" in cor- layer perpendicular to axial direction of pressure
rosion kinetics. This results from the same tubing).
corrosion rates on an identical specimen
surface. Therefore, the oxide front formed
during corrosion of a pretransition speci- ridges of oxides can be seen in posttran-
men is located at a constant level (from the sition specimens. These oxide ridges can
metal surface). Figure 8(c) is a higher-mag- deform and eventually destroy the protec-
nification micrograph showing the oxide tive oxide barrier layer [9], which is present
structure. at the oxide-metal interface.
Figure 9(a, b) shows the typical topog- The interface topography of specimens
raphies of posttransition specimens (i.e., with the oxide layer parallel to the axial
after "breakaway"), with oxide layers per- direction of the pressure tubing (i.e., axial-
pendicular to the axial direction of the radial sections) is shown in Fig. 10. Oxi-
pressure tubing. From Fig. 9 it can be seen dation proceeds along grain boundaries in
that the interface in the posttransition the same manner as in the specimens with
specimens is not straight but is rather jag- the oxide layer perpendicular to the axial
ged. This is due to variations in the cor- direction of the pressure tubing.
rosion rates. Where there are the highest Figure 11 presents micrographs of the
corrosion rates, there are "fingers" of oxide-metal interface formed on a Zr-
oxide that protrude from the general oxi- 2.5Nb alloy specimen after exposure to a
dation front. If one compares Fig. 8(b, c) 300°C pressurized lithiated water environ-
with Fig. 9(a, b), which show the oxide- ment for long corrosion times (500 h) (SEM
metal interface in the pretransition and specimen prepared using Method 2). It can
posttransition regions, respectively, long be seen that the microstructure of metal
SEM Cross-Sectional Specimen Preparation 31

Ax

Pre,

FIG, 10. Topography of the oxide-metal interface in a pretransition (short time

corrosion) specimen (oxide layer parallel to axial direction of pressure tubing).

close to the interface is different from that
far away from the interface. The metal
close to the interface has larger cx-grains
than that far from the interface. A possible
explanation is that either solution of oxy-
gen in the metal or oxidation of the metal
results in an expansion of the metal. Thus,
there may be an intermediate layer in the
metal close to the oxide-metal interface for
the posttransition specimens.

FIG. 11. Micrographs of (a) the oxide-metal interface and (b) the metal close to the interface on a Zr 2.5Nb
alloy specimen formed during exposure to a 300°C pressurized lithiated water environment for 500 h ISEM
specimen prepared using Method 2).
32
FIG. 12. Micrograph of the oxide-metal interface on
a pure zirconium specimen exposed to a 300°C pres-
surized lithiated water environment for 40 h (SEM
specimen prepared using Method 1).
Pure zirconium specimens exposed to a
300°C pressurized lithiated water environ-
ment for 40 h show a very different be-
havior, (see scanning electron micrograph
in Fig. 12). The oxide has a "nodular" ap-
pearance, rather than the elongated ap-
pearance in Zr-2.5Nb alloys. This is due
to the fact that in pure zirconium, there is
not the complex grain boundary structure
as in the Zr-2.5Nb alloys. Therefore, pref-
erential oxidation at the grain boundaries
is not observed when pure zirconium is ex-
posed to 300°C pressurized lithiated water.
Detailed corrosion mechanism(s) for a
FIG. 13. (a) and (b) Scanning electron micrographs of different areas of the same specimen with multilayers of
TiN (SEM specimens prepared using Method 2).
Y. Ding and D. 0. Northwood
number of different zirconium alloys will
be reported in a subsequent publication.
TiN COATINGS
SEM examination of TiN coated specimens
prepared using both Methods 1 and 2
showed that the TiN coatings were uni-
form and smooth (see Figs. 5 and 7). Film
adhesion to the substrate appeared to be
good, but a sharp interface was evident.
Examination of the SEM specimens pre-
pared using Method 2 showed that the
coating layer consisted of two layers [see
Figs. 6(b) and 7]. Adhesion between the
first layer and substrate or first and second
layers is good. Figure 13(a, b) shows typical
micrographs of different areas in the same
specimen with a multilayer TiN structure.
Although their total thicknesses are the
same ( - 5 I~m), their structures are differ-
ent. Figure 13(a) seems to contain two lay-
ers, whereas Fig. 13(b) seems to contain
three layers. This may arise from local
changes in deposition conditions. SEM ex-
amination of a TiN coated specimen with
a five-layer coating showed that the TiN
surface layer has a very fine grain size, and
the TiN layer close to the substrate has a
large grain size. A possible explanation for
this might be that the relatively thick in-
termediate o~-Ti layer formed next to the
S E M Cross-Sectional Specimen Preparation
steel substrate prevents the heterogeneous
structure of stainless steel from being re-
flected in the structure of the TiN surface
laver [12]. This demonstrates the need for
a better understanding of the relationships
between the microstructure and the pro-
cessing parameters.
CONCLUSIONS
SEM specimen preparation techniques
have been developed for the study of the
interfaces between substrates and coat-
ings/oxide films have been successfully ap-
plied to the study of TiN coated steel and
corroded zirconium alloys. The prepara-
tion technique, which utilizes a tapered
cross section, and which was developed
for examination of the oxide-metal inter-
face formed on zirconium and its alloys,
has potential application to other materials
containing an oxide-metal interface or
coating-substrate interface, provided a
suitable etching solution can be found to
etch back the metal or substrate until the
oxide-metal/coating-substrate interface is
reached.
This work was supported by the Natural Sci-
ences and Engineering Research Council of
Canada (Operating Grant A4391) and the
CANDU Owner's Group (COG) through
Working Party No. 35. Mr. John W. Robinson
assisted with the corrosion testing and with the
SEM examination. The Zr-2.5Nb pressure
tubing was supplied by Ontario Hydro,
Canada.
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