CHAPTER 3
Experimental Preparation
Proper preparation is critical to successful elec-
trochemical testing. This chapter examines specific
preparation procedures that will lead to a high de-
gree of reproducibility in electrochemical tests. Chap-
ter 3 is divided into three sections: Specimen
Preparation, Solution Preparation, and General Wir-
ing/Connections.
Specimen Preparation
Proper preparation and careful handling of the
working electrode specimen is critical in obtaining
reproducible results during electrochemical testing
Typically, electrochemical testing utilizes relatively
small test specimens, and test matrices do not pro-
vide for a large number of replicates. For these rea-
sons, specimen preparation is even more important
for electrochemical testing than it is for other types
of corrosion tests.
Surface Finish
The first thing to consider is the selection of a
surface finish. Two primary objectives of a surface
preparation procedure are:
(1) The surface will respond in electrochemical
tests in a manner similar to the response of
the commercially produced material in the
service of interest, and
(2) The procedure is convenient and practical.
29
The former consideration requires minimal dit-
ferences between the surface composition and struc-
ture of the test specimens and the material that will
be put into service. The latter consideration elimi
nates procedures difficult to reproduce and time-con-
suming procedures unless they are determined to
be absolutely necessary.
In general, the surface finish should be smooth
enough to obtain a uniform surface finish and not so
smooth that reproducibility is difficult to maintain. An
extremely smooth surface, as achieved by electro-
lytic polishing or even by mechanical polishing with
a diamond or alumina abrasive paste, typically is not
desirable. Such surfaces are not only more difficult
to reproduce because of the time and effort required,
but they often respond differently in the environment
than a commercial surface, e.g., as-rolled. An
electropolished surface may have a significantly dif-
ferent surtace composition than would be present on
commercially produced sheets, tubing, etc.
A surface roughness that corresponds to a 400
to 600-grit silica carbide grinding paper finish com-
monly is used in corrosion tests. Other consider-
ations, such as the desire to test as-received, finished
parts or welded specimens could be the controlling
factor. The most important aspect is that, within a
group of tests to be compared, the surface finish of
the specimens be similar.
CAUTION: If grinding paper is used for speci-
‘men preparation, it is necessary to use fresh pa-
per for each alloy.30
DC Electrochemical Test Methods
For example, grinding aluminum on the same
paper as steel will result in steel contamination of
the aluminum specimen surfaces. This may result in
the acceleration of the corrosion of the aluminum.
Grinding and polishing always affects the surface
layers of the metal by introducing cold work. The thick-
ness affected is a function of “severity” of grinding/
polishing and the grit size, etc. For this reason, it is
recommended that grinding operations be minimized
Only grind enough to remove prior machine marks
and use a ‘light touch”. Significant pressure is not
necessary for effective grinding,
An additional concern during surface finishing is
heat generation during grinding. Whenever possible,
wet grinding is used to maintain temperatures at an
acceptable level. If dry grinding is performed on a
belt or wheel, care must be taken to periodically cool
circumstances when intentional crevices are placed
‘on samples.
Degreasing
Once the surface finish is complete, the speci-
men should be washed well to remove any grit and
loose particles from the surface. Next, the specimen
should be degreased. ASTM Standard G5 suggests
degreasing by boiling for five minutes in benzene
followed by a distilled water rinse (deionized water is
acceptable as well). However, benzene is highly toxic
and must be used in a fume hood with extreme care
and is not generally recommended. A satisfactory
alternative is to degrease by immersion in acetone
for one to three minutes, preferably using an ultra-
sonic cleaner, followed by rinsing with distilled (deion-
ized) water. It is important not to handle specimens
with bare hands following degreasing. If the speci-
mens have been prepared previously and stored for
more than 48 hours prior to immersion into the test
cell, it is preterable to butt the surface briefly with the
final finishing paper (400-600 grit) and lightly rinse
with acetone followed by distilled (deionized) water.
Sometimes, the reproducibility of the measurements
is affected by the time between final finishing and
testing,
Mounting
Mounting of the specimen also is critical in ob-
taining high quality, reproducible results. The primary
concern is that the mounting procedure not alter the
electrochemical measurements. For meaningful re-
sults, the test specimen must behave as the alloy
would in service. Two important considerations in
selecting a mounting procedure are (1) a crevice is
not created during mounting of the specimen, and
(2) the mounting material used is inert in the envi-
ronment being tested.
Because of these considerations, a convenient
and commonly used specimen in electrochemical
studies is cylindrical with a hole drilled and tapped in
one end. The electrode holders use PTFE washers
or gaskets for the mating surface to the specimen
(Figure 2.12). Upon screwing the specimen onto the
threaded rod, the PTFE is compressed forming a tight
seal between the specimen, the gasket, and the
holder, which minimizes any crevice and provides a
suitable mounting arrangement for testing in most
aqueous environments,
At ambient temperature, hand tightening usually
is adequate with PTFE holders. In fact, over-tighten-
ing can produce an unwanted crevice due to defor-
mation of the PTFE (Figure 3.1). A further
consideration is high temperature (75-100°C) ambi-
ent pressure tests in which the PTFE can creep
(slowly deform) under mechanical load and loosen
the seal. Under these conditions, more pressure is
required to tighten the specimen than normal, or al-
ternative mounting procedures are required.
In many electrochemical tests, it is not possible
to use cylindrical or disc specimens. A number of cre-
ative mounting arrangements have been used. These
include:
+ rod or odd-shaped specimens masked-off
with a non-conducting, chemically resistant
coating to some distance below the solution/
atmosphere interface;
+ mounting specimens in various mounting
resins followed by grinding and polishing the
test surface of interest;Corrosion Testing Made Easy
31
Only Slight
Bulging NN
Edges Remain
Relatively Even
a. Proper Tightening
Working Electrode
lt
Severe
Bulging
\___vertap
PTFE
Spacer
b, Over -Tightening
FIGURE 3.1 - Proper tightening of the PTFE gasket.
+ clamping a cell down onto a specimen using
an o-ring or washer so the specimen
becomes the bottom of the electrochemical
cell; and
+ using a non-conducting, chemically resistant,
adhesive tape to mask off areas of a
specimen.
Coatings and mounting resins must be inert in
the test environment, and the coating must be resis-
tant to significant water permeation during the test
period. The use of o-rings, gaskets, and washers
(other than PTFE) typically will cause more of a crev-
ice than the preferred compression PTFE washer.
Tapes often have problems with disbonding although
3M Company makes an adhesive PTFE tape (3M
Scotch Brand tape #5480) that has been used with
some success. The gasket or coating must be suf
ciently inert so undesirable species are not leached
from the mounting material and affect the specimen
behavior. For example, some gaskets, o-rings, and
coatings may leach chloride and sulfur species into
the test solution and affect the specimen corrosion
behavior. Therefore, it is important to check out any
new arrangement or mounting material in preliminary
tests to ensure crevices are not created and the
mounting material is inert. Crevices are easily identi-
fied in preliminary tests by removing the working elec-
trode and examining it for crevice attack at the
specimen-gasket (or coating) interface or beneath the
gasket (or coating). Leaching of chemical species
from the gasket or coating is much more difficult to
discern, and this is why PTFE is the material of choice
whenever practical. Obvious changes in hardness or
color of the gasket or coating are clear signs the gas-
ket or coating has undergone degradation.
(European Studies in Philosophy of Science 10) Florian J. Boge - Quantum Mechanics Between Ontology and Epistemology-Springer International Publishing (2018) PDF