COLOR
-ETCHING
for Multiphase Steels
Asimple step-etching procedure with
comaion etching solutions has been
applied to reveal individual
iticrostructural constituents in some
of the high-strength steels of current
industrial interest.
‘Amar K. De, John G. Speer*,
and David K. Matlock*
Colorado School of Mines
Golden, Colorado
hase identification not possible with stan
dard black and white micrographs is often
possible with color micrographs. In spite
Of this, the high cost associated with color
processing and perceived difficulties in sample
preparation, have prevented color metalopraphy
from becoming standard quality control tcol to
support product assessment during production.
fowover, the cost reductions associated with
digital photography now enable color metallog,
raphy to be incorporated into laboratory assess-
ments of production-dependent microstructural
variations. Improvements in digital data storage
systems for standard light-optical microscopes en-
able acquisition of quality color micrographs at rea
sonable cost. Furthermore, color metallographic
‘echiniques have been developed and applied to as-
sess microstructures in a variety of systems,
Toillustrate potential applications of color met-
allography, this article considers microstructural
constituent identification in DP and TRIP high:
strength steels. It summatizesa simple color etching
procedure that has been found to consistently re-
veal the distinct microstructural constituents with
the help of light optical microscopy. The color mi-
crographs are reproduced here with the help of a
digital data storage system.
Advanced steels
High-strength shoot stee! products such as dnal-
phase (DP) and austenite containing transforma-
tion induced plasticity (TRIP) steels are now gaining
*Memberof ASM International
ADVANCED
‘Tempertare
“Time scond|
Time ons
Fig
‘TRIP microti
significant industrial importance for acivanced au
tomotive applications, Dual-phase steels contain a
fine dispersion of martensite ina fertite matrix, al-
though the microstructure is often quite variable
and may contain martensite, retained austenite,
peatlite, and bait.
TRIP sheet steels consist of ferit,bainite, marten
site, and substantial amounts of retained austenite
Allof these constituents are critical for developing
the forming.and service properties of DP and TRIP
steels, and hence accurate phase identification is
needed to characterize the important effects of al-
Joying and processing
‘Three different steel microstructures representa-
tiveof typical multiphase steal families were selected
for study. A conventional C Mn Si sheet steel for
production of both DP/TRIP microstructures, and
‘a medium-carbon low alloy steel bar were included.
As summarized in Table 1, several color etchants
or etching tecliniques have been developed for these
high strength stools, and they form the basis or the
approach reviewed here. The limitations described
inthe table are based on the authors’ experiences.
‘Multiphase microstructures
The base steel (0.19C, 1.5Mry 1.58i) for DP and
TRIP microstructures was available in the form of
1.2mm cold rolled sheet,
* Dua-phuse stel: The DP microstructure (ferrite
+ martensite) is usually procluced by annealing the
steel at an inter-critical temperature (e+ region)
and then rapidly cooling to room temperature. In
the present study, three different duual-phase mi-
MATERIALS & PROCESSES/FEBRUARY 2003
‘Shel meat eyes forthe production of a) dual phase and (8)Table 1 — Common tint etchants for multiphase steels and some limitations
‘Htching solutions
Tinting effects on microstructure
Limitations
2.5% Nital followed by 10% aqueous
Fenite off white, bainite, martensite
Bainite, pearite, carbides and martensite appear
sodium metabistlite" and peartedark austenite white. dark.
LePea® Terrteyellow /blue, bainite brown, Austenite and nudensitenct separately
Equal postions of solitons setained austenite and identifiable. Adltional hest treatment or seaming,
(@)!eaqueous sodium metabisullite martensite white electron microcopy ‘needed for identifying
(0)496Dieral ‘mustensite and austenite
494 Picraland Deaqueoussodiuin __ Ferte brown, maitensiteand ‘Austenite and mariensit not separately delineated
rmetabisulite austenite white.
294 Nita followed by heat tinting
Feit, bainiteare beige, austenite
purple, martensite darkblue,
‘Additional heat treatment steps.
{EGR Vir Voor angst Pro” ASM Dl, Mats Pt tn 199 Bruce, Bon en O Rowe aalagapr Gal towel >
fr dr ara Ses" ASM in, 202 FS. Leou ural of Mea, 2, 190, cL 3. Tn, P11 Baad EV Pra CayProf TIP Sleds a, B-
‘som 0,
crostructures were produced by annealing the sam-
ples at three different temperatures (750,775, and
800°C) for 300 seconds, and then quenching in
water. This procedure was expected to result in
controlled variations in the phase fractions and
compositions within the a+ yfield,
* Transformation-induced plasticity stels: To de-
velop the TRIP microstructure, the steel was an-
nealed at 775°C for 300 seconds and then cooled
rapidly to an intermediate temperature of 400°C
(above the Ms). The sample was then held for 300
seconds to allow for bainitic ferrite formation ac.
companied by carbon-rejection into the interlath
austenite, which stabilizes the austenite during
rapid cooling to room temperature. The schematic
annealing cycles followed are shown in Figute 1.
‘The low alloy steel bar was normalized at 840°C
for one hour after hot rolling.
Etching solutions andl procedure
‘The following etching solutions were selected:
14% picral (4 gm diy picricacid in 100 ml ethan
col), mixed with few drops of concentrated hydro-
hltieacid (1m poe 100m of piral solution) and
10% aqueous sodium metabisullite solution.
‘The purpose of the hydrochloric acid was to im-
prove grain boundary etching and sharpen the ap-
pearance of iton carbides.
‘The steel cross-sections were mounted in phe
nolic resin (bakelite), mechanically ground with 120
through 600 grit paper, polished with 6 um dia~
mond and then finally polished to. scratch sree
condition with 1 rm diamond. After polishing with
diamond paste the surfaces were cleaned with soap
solution, water, and then alcohol. The surfaces were
dried with hot air.
Ina two-stage step-eiching procedure, the sam
ples were first clipped in the picral solution for 18
fo 20seconds for DPand TRIP steels, and 45 to 60
seconds for the alloy steel. During the whole etching,
process, the samples were gently oscillated. After
etching in picral, the samples were immediately
washed with water followed by ethancl and then
were blown diy in hota
Picral waschosen over nital because of better de-
lineation of carbides and bainite with picral. Nital
attacks ferrite grains and grain boundaries, but pi
«ral attacks interfaces between ferrite and carbide.
‘Therefore, the carbides are better revealed by picral
‘Once the microstructural observation was com-
pleted afier the first stage of etching, the samples
‘wore further dipped in freshly prepared sodium
metabisulfte solution for six to eight seconds. They
‘were immediately washed with water followed by
cethanol,and then dried in hot air. The soaking time
‘withsodiumn metabisulfite was critical, because over-
‘exposure to the solution led to excessive tinting, of
martensite and eventual blackening ofthe ferrite,
Microscope observations
‘The samples were examined with an Olympus
PMG: light optical microscope equipped witha
high resolution DP-12 digital camera (35 mm)
ystem. The digital camera is directly interfaced
th a computer that allows the color micrographs
to be downloaded in digital formats (jpeg, tiff)
‘The color micrograph files can either be printed by
color printers, or can be taken to any commercial
photo-shop for color printing,
For examination with the scanning electron mi-
‘roscope (SEM) at higher magnification, selected
samples previously examined in alight microscope
were further etched with 2% nital solution (2 ml
concentrated nitric acid in 98 mi ethanol), without
an intermediate polishing step. The amount of re-
tained austenite was measured in some instances
by X ray diffraction by copper Ka radiation. Thoin
tegrated intensities of diffraction peaks 220}, (311),
(21 Tjq and (200)_ were measured and the volume
fraction of austenite was then calculated by the di-
rect comparison method. In addition, individual
shases were measured for microhardness witha
‘ickers 10 gf load, to confirm the metallographic
phase identification results,
DPsteel microstructure
Figure 2a shows the microstructure after the first
etching step of the dual-phase steel quenched from
‘SIPC. The micrograph clearly reveals undissolved
carbides and traces of pearlite within some carbide
structures. Martensite or austenite is not revealed
at this siage, though these constituents appear as
relief at the grain boundaries. Figure 2h isthe sec-
‘ondary electron image of the same sample from the
SEM, revealing the same microstructure details.
igure 2c shows the microstructure after the
ADVANCED MATERIALS & PROCESSES/FEBRUARY 2003Fig. 2— Microstructure of dua-phasestet quenched from 750°C (a afer
rst stage etching reoealing pearte and wssotoe ones in the fer-
rite matrix, JOOOX, () searing electron image ofthe same sane and (c) microstructure afer second etdring step with sodium metabsulfite re-
ealing martensite (sraw-eoloed), ustette (ite), pearlte and undiseloed caries (bu
second stage of etching, It clearly reveals
straw-colored martensite at the grain
boundaries and also within the carbide
regions, Retained austenite appears as
small white particles at grain bound-
aries and also within the carbide-
pearlite conglomerate. The micrograph
in Figure 2calso reveals that the tintetch
distinctly distinguishes the martensite
from austenite in some of the M-A con-
stituent islands as marked in the
micrograph.
After the two-stage etching process,
Fig. 3a and 3b reveal the microstriic-
tures of two other dual- phase steels,
quenched from. 775 and 800°C, respec-
tively. The straw-colored martensite is
distinctly revealed, and the retained
austenite appears as small bright white
particles mostly associated with marten-
site. Carbides were hardly detected in
these two steels. The distinct color con-
‘rast between the martensite and the fer-
rite matrix also enabled meastirement
of the volume fraction of marter
through image analysis, and the
‘martensite fractions were found to be
43% and 52% respectively. Retained austenite was
measured by X-ray diffraction and was found to
be 18 to 2%,
(One important revelation from the above etching
experiment with three different DP steels is that the
characteristic tinting of martensite was quite con
sistent despite significant differences in the com-
position and volume fraction of the martensite.
TRIP steel microstructure
Figures da and 4b show the TRIP steel mi-
crostructure after the two etching stages. The bai-
nite is clearly delineated in the form of angular or
acicular patterns. (In these silicon-containing steels,
carbicie-free austenite containing bainite mi-
crostructures re found. They consist of bainitie fer-
rite laths, not apparent in Fig. 4, and interlath
austenite, which is apparent and highlights the aci
cular morphology.) Martensite and austenite are
not differentiated clearly at this stage.
‘Thesecond siage etching with sodium metabisul-
fite tints the martensite, and the austenite remains
unaffected, The final microstructure (Figure 4b)
shows the martensite in its typical straw color, and
therefore martensite can be identified separately
ADVANCED
Fig. 3— Microstructures of dual-yhase steels quenched from (a) 77
secondetching step receaing mumtensit (strxo-oloed) ane fne retained austenite grains (whit)
itv the ferrite matrx, 10Q0X. No carbides are present in these spe
lack, 1000X.
from austenite. Overexpostre to the second stage
of etching darkens the martensite and makesit dif-
ficult to distinguish from bainite
‘The austenite is somewhat brighter or whiter
than the ferrite andl listinetly delineated from the
fertite due to the addition of hydrochloric acid. The
volume fraction of retained austenite was measured,
to be about 10% by X-ray diffraction in this steel
Low-alloy steel
‘The effectiveness of the step etching procedure
‘was further substantiated during microstructure
characterization of an alloy steel. Figure 5a shows
the microstructure of the medium-carbon alloy steo!
after the first stage of etching, The steel apparently
represented complex ferritic pearlitic bainitic mi-
crostructure, The picral-etching distinctly revealedt
the pearite (massive dark regions) and bainite (ina
granular bainite morphology) constituents
‘The microstructure observable at this etching
stage also revealed the presence of a band con:
taining some other constituents that are not clearly
identifiable at this stage. The second stage tint
etching revealed these constituents to include
martensite, identified by its characteristic straw.
MATERIALS & PROCESSES/FEBRUARY 2003
75 ane (6) BPC eer the
te ard martestesterie cud (1) afr the second etcang step realty martensite (stnew-