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Electrolytic Etching in Welding Metallography: Research
Electrolytic Etching in Welding Metallography: Research
Marek St. Węglowski PhD Eng. - Instytut Spawalnictwa, Zakład Badań Spawalności i Konstrukcji
Spawanych / Testing of Materials Weldability and Welded Constructions Department
No. 2/2013 BIULETYN INSTYTUTU SPAWALNICTWA 5
One of the most popular theories explain- ries have been developed in order to explain
ing the phenomenon of electrolytic etching/ this and other phenomena. Yet they all share
electrolytic polishing is the theory devel- the same disadvantage, i.e. they explain
oped by Jacquet [3], according to which phenomena in a temporary manner and are
etching/polishing is caused by the anodal usable only in individual cases [3].
action of electrolyte on, first of all, the
peaks of surface roughness of a metal sub- Factors affecting electrolytic
jected to etching/polishing and, to a lesser etching conditions
degree, on cavities. Such diversified dis- The most important factors affecting
solving can be explained by the formation etching conditions include the potential dif-
of an anode film known also as a viscose ference (PD) and the density difference of
film. This film covers the metal surface, current, electrolyte temperature, electrolyte
with projecting surface roughness peaks be- stirring, surface pre-treatment, heat treat-
ing covered by a thinner film layer than the ment of the specimens, treatment time, di-
cavities (Fig. 2). The resistance of the thin- mensions of the electrolyser used for etch-
ner film layer (on the peaks) is lower than ing and electrolyte consumption degree.
that of the thicker film layer (in the
cavities). Difference of current potentials and
density
Usually during electrolytic etching it is
possible to obtain better results if during the
process the difference of potentials is per-
manently monitored rather than the densi-
ty of current. Independent of the difficulty
in maintaining constant current density, a
Fig. 2. The formation of anode film and distribution of
ions in the inter-electrode space [3]
longer time of electrolysis combined with
heightened current density cause the emis-
For this reason the peaks of surface sion of a gas which may trigger the forma-
roughness dissolve to a greater extent than tion of pits on the surface of a specimen.
the cavities. In this manner, the surface ir- Moreover, at the initial stage of anodal dis-
regularities are gradually made even until solving, prior to the stabilisation of etching
polishing or etching. This theory clarifies conditions, current density should signifi-
the basic course of electrolytic etching or cantly exceed the normal value for a peri-
electrolytic polishing, yet it does not ex- od sufficient for the stabilisation of etching
plain individual cases. The Jacquet theory conditions. It is important that at the initial
is right only for a certain group of phenom- stage of etching the difference of potentials
ena; it properly explains the processes of on the electrolyser should be within the
electrolytic etching/electrolytic polishing boundary values used for etching.
of copper and steel in an electrolyte com-
posed of phosphorus acid and organic ad- Temperature of electrolyte
ditions as well as electrolytic etching/ elec- The resistance of the electrolyte decreas-
trolytic polishing of steel in a chloric-acetic es along with an increase in temperature.
electrolyte. In these cases one can observe Consequently, the voltage necessary for ob-
the formation of a dense colloidal or liquid taining the same current density decreases.
film from the reaction products. Many theo- The voltage corresponding to a given cur-
6 BIULETYN INSTYTUTU SPAWALNICTWA No. 2/2013
rent density is defined by an experimentally face of objects subjected and those unsub-
determined equation: jected to heat treatment. The heat treatment
has a positive effect on the quality of the sur-
K
U= face intended for etching, provided it has led
a ×T + b to the formation of a uniform structure. If a
where: heat treatment has triggered the formation of
K, a, b – constants dependent on electrolytic carbides, as is the case with alloy steels dur-
conductance, electrolyser dimensions and ing electrolytic etching for instance, the so-
current flowing through the electrolyser, called point corrosion may occur as a result
T – temperature. of the intense dissolving of areas around the
The equation reveals that the power nec- carbides.
essary for maintaining given current density
decreases along with an increase in temper- Etching time
ature [1]. The time of electrolysis necessary for ob-
taining the desired condition of the surface
Electrolyte stirring changes depending on a metal and electro-
During the process of electrolysis in stabi- lyte used. According to a general principle,
lised conditions, the products of the reaction the time of etching is inversely proportional
accumulate around the electrode. In some to current density. In this manner, in the case
cases the inflow of fresh electrolyte is insuf- of solutions containing orthophosphorous
ficient , and stirring is necessary to remove acid, for which low current density is used,
some of reaction products. However, one the treatment requires a longer time than in
should avoid excessive stirring as it could the case of the solutions of tetraoxochloric
destroy the film and prevent the stabilisation acid, for which high values of current densi-
of optimum etching conditions. Moving and ty are usually used. In general, etching lasts
stirring also prevents excessive local heat- between several seconds and several minutes
ing caused by the flow of current through [1].
the high-resistant layers on the anode and
favours maintaining a more uniform electro- D imensions of elec t rolyser for
lyte temperature. In many cases the best re- e tching
sults are achieved by rotating and swinging An important factor associated with elec-
the anode rather than by stirring the solution. trolytic etching is the dimensions of an elec-
trolyser, as their changes may significantly
Impact of heat treatment on the out- affect the process conditions.
come of electrolytic polishing
The structure of metal significantly affects Impact of electrolyte consumption
its properties and consequently its behav- During etching iron, for example, the con-
iour during treatment. This impact is visible tent of Fe ions in the electrolyte increases
during mechanical working and in particular gradually as the amount of metal deposit-
during electrolytic etching. The change of the ed on the cathode is much smaller than the
structure and of the mutual relations of indi- amount obtained from the dissolved anode.
vidual components causes changes both in Depending on the shape and dimensions of
the potential and dissolving degree, affect- the cathode, this amount makes up 5% - 15%
ing the surface appearance. The difference is of the dissolved anode metal. An increase
particularly evident while comparing the sur- in electrolyte density is accompanied by
No. 2/2013 BIULETYN INSTYTUTU SPAWALNICTWA 7
a worsening quality of the surface subject- the surface of a metallographic specimen.
ed to etching. In consequence, the solution This can easily be observed if upon changing
becomes useless. Although a slight etching the abrasive paper grade one also changes
effect can be observed, the phenomena ac- the grinding direction by an angle of 10°-
companying the process render the micro- 20°. During grinding with abrasive papers it
scopic observation of the etched specimen is necessary to neither deform nor overheat a
difficult. The etching ability of the solution specimen being ground. For this reason it is
can be slightly extended by using a slightly advisable to wet grind specimens using wa-
higher current density or by adding between ter-resistant abrasive paper and devices en-
5 ml and 10 ml of distilled water per one suring permanent wetting of a grinding area
litre of solution. A greater amount of water [4]. The process of precise grinding finishes
also worsens the etching effect. with abrasive paper of a granularity depend-
While using chemical or electrochemical ent on the type of a material out of which a
etching one should bear in mind that used given specimen is made. It is assumed that
chemicals ought to be disposed of in accord- such granularity should amount to 600 for
ance with environmental protection regula- steels and 1000 for non-ferrous metals.
tions. The process of mechanical polishing is
carried out with a rotating disk covered with
Preparation of specimens for electro- a special cloth, onto which one applies di-
lytic etching amond-based polishing materials of various
The quality of an electrolytically etched gradation (e.g. 6÷0.25 μm). Polishing usually
surface is much more dependent on the finishes with liquid slurry of aluminium ox-
stage of mechanical polishing and grinding ide Al2O3 (grade e.g. 0.25 μm). The proce-
than that obtained through chemical etching. dure of polishing is strictly dependent on the
Electrolytic etching is a process which can type of a material being treated. The selec-
be initiated only at a certain specified surface tion of optimum conditions requires prelimi-
roughness. If the roughness is too high even nary tests. It may happen that due to improp-
properly selected process conditions will erly selected mechanical treatment, scratches
not result in a properly etched surface (the after electrolytic etching are not removed
process of electrolytic etching ”highlights” but, on the contrary, become more visible. In
scratches formed as a result of mechanical such a case, the scratches that are revealed
polishing). This is probably because the film, are those which during polishing were cov-
instead of filling the surface cavities, covers ered up by metal, which during electrolytic
both the peaks and the cavities with the lay- etching are dissolved more intensively than
er of the same thickness. While considering the remaining part of the specimen [3].
the applied gradation of abrasive paper, pri- A better effect from electrolytic etching is
or to electrolytic etching surfaces should be achieved sooner if the surface to be etched
precisely ground using abrasive paper, start- is better prepared in the process of mechan-
ing with the paper of the greatest granulari- ical polishing. Objects intended for electro-
ty (e.g. 80 or 100), and next using paper of lytic etching should be carefully cleaned and
lower granularity (280, 500, 800 etc.) Each degreased. If impurities such as aluminium
grade of abrasive paper should be used until oxide Al2O3 remain, the films floating on the
all marks (especially scratches) coming from surface may disturb treatment by causing
previously conducted grinding with the pa- the formation of stains on the surface being
per of a greater granularity are removed from polished.
8 BIULETYN INSTYTUTU SPAWALNICTWA No. 2/2013
An indication of properly conducted de- A simple easy-to-use design guarantees
greasing is uniform water wetting of the failure-free operation also for less experi-
whole specimen surface after its rinsing. Theenced personnel. This is a unique selling
specimen should be subjected to electrolytic point and a competitive edge over devices
etching immediately after the last rinsing asoffered by other companies. A person car-
it prevents accidental soiling and corroding rying out tests can precisely adjust etching
of the surface [3]. time and voltage.
The device for electrolytic etching Elek-
Exemplary results of electrolytic troMat ET1 can be used in the following in-
etching stitutions:
Table 1 presents examples of electrolytic • metallographic laboratories of universities
etching results (device ElektroMat ET1). and research institutes,
Table 1. Exemplary results of electrolytic etching