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ASM Handbook, Volume 9: Metallography and Microstructures
G.F. Vander Voort, editor, p644–669
DOI: 10.1361/asmhba0003766
Metallographic
Techniques for Tool Steels
George F. Vander Voort, Buehler Ltd.
TOOL STEELS can be prepared for macro-
scopic and microscopic examination using the
same basic procedures used for carbon and al-
loys steels. However, because many tool steels
are highly alloyed and are generally heat treated
to much higher hardness than most carbon and
alloy steels, specific aspects of their preparation
differ slightly. The reasons for these differences
and the required procedural modifications are
discussed in the following sections. Also cov-
ered are the effects of hot working, composition,
austenitizing, and tempering on microstructure.
Macroexamination
Specimen selection is generally based on the
original ingot locations. Sampling is usually per-
formed after primary hot working to billet or
bloom shapes. Disks 12 to 25 mm (0.5 to 1.0 in.)
thick are most often cut from billet or bloom
locations corresponding to the top and bottom of
the ingot. They are sometimes cut from the mid-
dle location. The hardness of these products can
be rather high, unless the billet or bloom was
subjected to a full annealing cycle. Thus, sec-
tioning of such specimens may be more difficult
than for carbon or alloy steels. For most work,
transversely oriented disks (perpendicular to the
Fig. 1 AISI W1 tool steel austenitized at 800
C (1475
F), brine quenched, and tempered 2 h at 150
C (300
F). Black rings are hardened zones in 75, 50, and 25 mm (3, 2, and
1 in.) diameter bars. Core hardness decreases with increasing bar diameter (all one-half actual size). (a) Shallow-hardening grade. Case, 65 HRC; core, 34 to 43 HRC. (b)
Medium-hardening grade. Case, 64.5 HRC; core, 36 to 41 HRC. (c) Deep-hardening grade. Case, 65 HRC; core, 36.5 to 45 HRC. Hot 50% HCl
hot working axis) are preferred. However, lon-
gitudinal disks are better suited to studying de-
formation fiber or segregation. Transverse disks
are preferred for general-quality evaluations. If
very hard, the disks should be tempered before
etching. For routine-quality studies, a saw-cut
surface is adequate. If better resolution of detail
is required or if photography is to be conducted,
surface grinding is performed after cutting.
Macroetching. The macroetchant most
widely used to evaluate macrostructural quality
of tool steels is the standard immersion solution
of equal parts of hydrochloric acid (HCl) and
water at 70 to 80
C (160 to 180
F) for 15 to 45
min. Such etching will reveal segregation,
cracks, porosity, inclusions (manganese sulfides,
for example), flow lines, surface decarburization
or carburization, and hardness variations. Inter-
pretation of results is aided by referring to stan-
dard charts (Ref 1–4). Figure 1 illustrates the use
of the 50% hot HCl macroetch to reveal the case
depth in different sized brine-quenched and tem-
pered specimens of W1 tool steel with three lev-
els of hardenability. Note that there is excellent
contrast between the hardened case and the non-
hardened core.
This etching procedure can be used to evaluate
disks cut from sections smaller than billets or
Copyright © 2004 ASM International®
All rights reserved.
www.asminternational.org
disks cut from failed components; however,
room-temperature macroetching, which is also
quite common, often uses a 10% aqueous nitric
acid (HNO3) solution. Smooth-ground speci-
mens are immersed for up to a few minutes in
this solution to reveal such surface conditions as
decarburization, carburization, nitriding, hard-
ened layers, and grinding damage. Internal qual-
ity problems, such as segregation, are revealed
but usually less effectively than by hot-acid etch-
ing. After etching, the surface is washed,
scrubbed to remove etching smut, and dried.
Etching of small polished sections in 2 to 5%
nital will also bring out surface conditions that
cannot be as clearly revealed by the cold 10%
aqueous HNO3 solution. However, nital is less
effective on a smooth, ground surface. Figure 2
shows the carbide distribution on longitudinal
planes of M2 and T1 high-speed steels revealed
by macroetching discs of varying diameter with
10% nital. Figures 3 and 4 show the carbide seg-
regation by light microscopy examination in
three of the sizes for the M2 and T1 discs.
The sulfur print test (Ref 5, 6), another prev-
alent technique, is used to evaluate the distri-
bution of manganese sulfides. Fracturing of
hardened transverse etch disks is also performed
to detect oxide inclusion stringers or graphite on

the longitudinally oriented fracture. The fracture
surface is often heated to produce a blue temper
color, because the uncolored oxides exhibit
strong contrast against the dark fracture.
Fig. 2 Carbide distribution on longitudinal planes of high-speed steels revealed by macroetching discs of varying
diameter with 10% nital. (a) M2 tool steel. (b) T1 tool steel. Both 1⳯
Fig. 3 AISI M2 round bars. Carbide segregation at the center of round bars of different diameters. (a) 27 mm (11⁄16 in.) diam. (b) 67 mm (25⁄8 in.) diam. (c) 105 mm (41⁄8 in.) diam.
10% nital. 100⳯
Metallographic Techniques for Tool Steels / 645
Microexamination
Sectioning. Relatively soft specimens (less
than 35 HRC) can be cut using band saws or
hacksaws. However, such operations produce a
substantial zone of deformation beneath the cut
and rather rough surfaces. Thus, the initial rough
grinding with a coarse abrasive (80- to 120-grit
silicon carbide, for example) must remove this
damage. However, such coarse abrasives gener-
ate large amounts of damage. Sectioning with an
abrasive wheel developed for metallography is
recommended, because it produces less damage
and yields a better surface finish, so that dam-
aging, coarse abrasive grinding can be mini-
mized or eliminated. Then, a somewhat finer
abrasive, which generates less damage, can be
used for the first step (often called planar grind-
ing with automated, multispecimen preparation
systems). This procedure facilitates generation
of a correctly prepared surface so that the true
microstructure can be observed.
Higher-hardness specimens must be cut using
water-cooled abrasive cutoff wheels. The blade
should have a “soft” bond (that is, it breaks down
readily, exposing fresh abrasive to the cut) for
effective cutting and avoidance of burning. Ef-
fective water cooling limits heat generation but
is inadequate by itself if the wrong blade is used,
that is, a blade that does not break down at the
proper rate. Dull abrasives generate excessive
heat and damage in cutting. Cutting as-quenched
specimens is very difficult without introducing
some damaging heat that may cause burning or
cracking. Cutting quenched and lightly tempered
tool steels is much easier but still requires use of
a wheel designed for such steels. Heat generated
by improper technique can produce a highly tem-
pered appearance in the martensite and, if heat-
ing is excessive, can re-austenitize the surface.
In extreme cases, melting can occur at the sur-
face, with an extensive heat-affected zone below
this area. Subsequent grinding steps cannot eas-
ily remove such damage without introducing
more damage.
When working with as-quenched high-alloy
tool steels, it may be helpful to fracture the spec-
646 / Metallography and Microstructures of Ferrous Alloys

Fig. 4 AISI T1 round bars. Carbide segregation at the center of round bars of different diameters. (a) 35 mm (13⁄8 in.) diam. (b) 64 mm (21⁄2 in.) diam. (c) 83 mm (31⁄4 in.) diam. 10%
nital. 100⳯

imen. This will produce a flat, damage-free sur- However, some mounts have poor resistance to ture, transparent methyl methacrylate compres-
face due to the extreme brittleness of such steels. solvents such as alcohol, and most polymeric sion-mounting thermoplastic material can be
The fractured surface can then be carefully mounts are badly degraded if heated etchants are used. Somewhat better results can be obtained
ground, with adequate cooling, and polished for required. The compression-mounting epoxies using cast, “cold”-mounting epoxy resins.
examination. prevent these problems. If a transparent mount Casting epoxies are the only materials that
For high-hardness, high-alloy steels, section- is required to control grinding to a specific fea- produce true adhesive bonding to the sample.
ing with a low-speed saw or with a linear-pre-
cision saw at higher rotational speeds, with alu-
mina wafering blades, diamond, or cubic boron Table 1 Five-step preparation practice for tool steels
nitride non-consumable blades, can provide Load
Speed,
high-quality surfaces with minimum cutting-in- Surface Abrasive/size N lbf rpm/direction Time, min
duced damage. Although the cutting rate is
Waterproof grinding 120/P120- to 240/P280-grit SiC, 22–27 5–6 Comp Until plane
slower than with an abrasive cutoff saw, such paper (or equivalent) water cooled
surfaces are smooth, damage is minimal, and Silk cloth or rigid 9 lm diamond (with lubricant) 22–27 5–6 Comp 5
grinding can begin with rather fine grits (320- or grinding disk
400-grit silicon carbide, for example). Section- Woven (napless) or 3 lm diamond (with lubricant) 22–27 5–6 Comp 3
pressed cloths
ing is a violent process, and excessive damage Woven or pressed cloths 1 lm diamond (with lubricant) 22–27 5–6 Comp 2
introduced in sectioning rarely is removed fully Medium-nap cloth 0.05 lm colloidal silica or sol- 22–27 5–6 Contra 1.5–2
by the preparation method. gel-type alumina suspensions
Mounting. Bulk samples frequently can be
polished without mounting. Coding of un-
mounted specimens is generally limited to a few Table 2 Four-step preparation practice for tool steels
stamp marks (if the steel is soft enough to Load Speed,
stamp), such as a job number. Vibratory scribers Surface Abrasive/size N lbf rpm/direction Time, min
can be used, but subsequent corrosion may make
Waterproof grinding 120/P120- to 240/P280-grit SiC, 27 6 240–300 Until plane
these marks hard to read. Most modern auto- paper (or equivalent) water cooled Comp
mated grinding/polishing devices can handle un- Rigid grinding disk (or 9 lm diamond suspension (with 27 6 120–150 5
mounted specimens. If edge retention is impor- woven cloth) lubricant) Comp
tant, mounting is recommended. Plating the Woven (napless) or 3 lm diamond (with lubricant) 27 6 120–150 3
pressed cloths Comp
surface prior to mounting (Ref 5) produces ex- Medium-nap cloth 0.05 lm colloidal silica or sol- 27 6 120–150 2
cellent results but is not always necessary. Com- gel-type alumina suspensions Contra
pression-mounting epoxy resins with fillers pro-
vide excellent edge retention, even with
nonplated specimens. Automated grinding/pol- Table 3 Three-step preparation practice for tool steels
ishing devices, rather than hand polishing, yield
Load
much better edge retention. Modern practices us- Speed,
Surface Abrasive/size N lbf rpm/direction Time, min
ing napless polishing cloths provide excellent
edge retention. Rigid grinding disks produce su- Waterproof paper (or 120/P120- to 320/P400-grit SiC, 27 6 240–300 Until plane
equivalent) water cooled Comp
perb edge retention. Hard or soft rigid 3 lm diamond suspension 27 6 120–150 5
For small or oddly shaped specimens, mount- grinding disks Comp
ing is preferred. If the edge is not of particular Medium-nap cloth 0.05 lm colloidal silica or sol- 27 6 120–150 5
interest, most mounting media are satisfactory. gel-type alumina suspensions Contra
 Metallographic Techniques for Tool Steels / 647

When used correctly, they produce the lowest
heat during polymerization and are useful when
the specimen cannot tolerate the higher heat
used in compression mounting. However, con-
siderable heat can be generated during poly-
merization of epoxy resins if the process is not
Polishing is most commonly performed using
one or more diamond abrasive stages, followed
by one or more final abrasive stages. For routine
Table 4 Microstructural etchants for tool steels
Etchant
work, polishing with 9 and 3 lm diamond abra-
sives is generally adequate. The diamond abra-
sive may be applied to the polishing cloth in
Comments

controlled properly. Cast acrylic resins generate
substantial heat, because they polymerize in less
than 10 min. When edge retention is not re-
quired and heat degradation is not anticipated,
low-cost phenolic compression-molding mate-
rials can be used, although they are badly de-
graded by boiling etchants. Identification marks
are easier to add on the back of a mounted spec-
imen than on a nonmounted specimen. Non-
mounted specimens degrade polishing cloths
faster than mounted specimens.
Grinding is performed in the same manner
as for carbon and alloy steels. Various manual
or automated devices may be used. Water-
cooled silicon carbide paper (200 to 300 mm,
or 8 to 12 in., diameter) is used, although alu-
mina-coated paper is preferred for ferrous alloys
(but is not as readily available). The initial grit
size selected depends on the technique used to
generate the cut surface. Historically, the usual
grit sequence is 120-, 240-, 320-, 400-, and 600-
grit with the American National Standards In-
stitute/Coated Abrasives Manufacturers Institute
scale (P120, P280, P400, P600, and P1200 for
the Federation of European Producers of Abra-
sives scale). Modern preparation procedures
(Tables 1–3) use a single SiC (or alternative sur-
face) grinding step. Grinding pressure should be
moderate to heavy, and grinding times of 1 to
2 min are typical to remove the scratches and
deformation from the previous step. Fresh paper
should be used; worn or loaded paper will pro-
duce deformation. Wheel speeds in grinding are
generally in the range of 240 to 300 rpm.
1–10 mL HNO3 and 99–90 mL
alcohol
4 g picric acid and 100 mL ethanol
1 g picric acid, 5 mL HCl, and 100
mL ethanol
10 g picric acid and 100 mL ethanol
2 g picric acid, 25 g NaOH, and 100
mL H2O
10 g K3Fe(CN)6 (potassium
ferricyanide), 10 g KOH or NaOH,
and 100 mL H2O
1 g CrO3 and 100 mL H2O
10 mL H2O2 (30%) and 20 mL 10%
aqueous NaOH
4 g KMnO4 (potassium
permanganate), 4 g NaOH, and
100 mL H2O
4 g NaOH and 100 mL saturated
aqueous KMnO4
Saturated aqueous picric acid plus
small amount of wetting agent
50 mL cold saturated aqueous
Na2S2O3 (sodium thiosulfate) and 1
g K2S2O5 (potassium metabisulfite)
1 g Na2MoO4 (sodium molybdate)
and 100 mL H2O
3 g K2S2O5, 10 g anhydrous
Na2S2O3, and 100 mL H2O
Note: When water is specified, use distilled water.
Nital. Most commonly used etchant. Do not store solutions with more than 3% HNO3
in ethanol. Reveals ferrite grain boundaries and ferrite-carbide interfaces in
annealed sample. Preferred etchant for martensite. Reveals prior-austenite grain
boundaries in as-quenched and lightly tempered high-alloy tool steels. 2–3% nital
most common; 5–10% nital used for high-alloy grades. Use by immersion.
Picral. Recommended for annealed structures or those containing pearlite or bainite.
Does not reveal ferrite grain boundaries in annealed specimens. Etching response
improved by adding 10–20 drops zephiran chloride. For high-alloy grades, add 1–5
mL HCl to improve etching response. Use by immersion.
Vilella’s reagent. Used in the same manner as picral or picral plus HCl
Superpicral. Must be heated to dissolve picric acid. Use by immersion, up to 1 min or
more. A few drops of HCl may be added to increase etch rate.
Alkaline sodium picrate. Immerse sample in boiling solution for 1–15 min or use
electrolytically at 6 V dc, 20
C (68
F), 30–120 s, stainless steel cathode. Colors
cementite and Fe4W2C
Murakami’s reagent. Use by immersion, fresh solution, hot or cold, up to 10 min.
Cold darkens chromium carbides and tungstides; cementite not attacked. Hot attacks
cementite.
Electrolytic etch, 2–3 V dc, 20
C (68
F), 30 s, stainless steel cathode. MC and M7C3
darkened; Mo2C outlined
Immerse 10 s at 20
C (68
F). Fe2MoC, Mo2C, and M6C outlined (latter also colored)
Groesbeck’s reagent. Immerse at 20
C (68
F). Fe2MoC and M4C outlined and
colored (blue and brown, respectively), Mo2C colored brown, (Fe,Cr)23C6 attacked
but (Fe,Mo)23Q not attacked
Immerse at 20
C (68
F). Mo2C and M7C3 attacked; M6C outlined and colored brown
Prior-austenite grain-boundary etch for hardened steels. Many wetting agents can be
used; sodium tridecylbenzene sulfonate most commonly used. Use at 20 to 100
C
(68 to 212
F) by immersion for 2 to 60 min. Addition of approximately 1% HCl
useful for higher-alloy grades. Room-temperature etching most common. Etching
with solution in a beaker in an ultrasonic cleaner works well. Lightly backpolish to
remove surface smut.
Klemm’s I (tint etch) reagent. Immerse (never swab) at 20
C (68
F) for 40–100 s to
color ferrite (blue or red) and martensite (brown). Cementite and austenite
unaffected
Beraha’s tint etch for cementite. Add 0.2–0.3 g NH4F•HF (ammonium bifluoride).
Add HNO3 to produce a pH of 2.5–3.0. Preetch sample with picral. Colors Fe3C
yellow-orange. Immerse up to 60 s; never swab.
Beraha’s tint etch. Immerse (never swab) until surface is colored red-violet. Colors
ferrite, martensite, bainite, and pearlite. Cementite unaffected

Fig. 5 AISI W2 (1.05% C), spheroidize annealed. (a) Etched with 4% picral to outline only cementite (uniform dissolution of the ferrite matrix). (b) Etched with 2% nital, which
reveals ferrite grain boundaries and outlines cementite. Note that the ferrite in some grains is weakly attacked, and the carbides within these grains are barely visible. (c)
Etched lightly with 4% picral, then tint-etched with Klemm’s I reagent to color the ferrite (blue and red). 1000⳯
648 / Metallography and Microstructures of Ferrous Alloys

paste, slurry, or aerosol form. Charging a new
cloth with paste, however, is most effective, be-
cause the removal rate is high as soon as polish-
ing starts. For the diamond abrasives, low-nap
or napless cloths are preferred. A lubricant, or
extender, compatible with the diamond abrasive
should be added to moisten the cloth and mini-
mize drag. Wheel speeds of 100 to 150 rpm and
moderate pressure should be used. Polishing
times depend on the number of steps in the pro-
cedure and the nature of the alloy (composition
and heat treatment condition).
Final polishing can be conducted manually or
automatically, using various devices. Alumina
abrasives, generally 0.3 lm alumina (A12O3)
and 0.05 lm c-Al2O3, have been widely em-
ployed with medium-nap cloths for final polish-
ing. Colloidal silica (SiO2, with a particle size
range of 0.02 to 0.06 lm) is also very effective
(Ref 5). Wheel speeds, pressure, and times are
the same as for rough polishing with diamond
abrasives. In general, tool steels are relatively
easy to polish to scratch-free and artifact-free
condition due to their relatively high hardnesses.
Table 1 lists a contemporary five-step practice
for preparing tool steels; Table 2 lists a contem-
porary four-step practice using a rigid grinding
disk; and Table 3 lists a three-step practice using
a rigid grinding disk. All methods produce ex-
cellent results.
In these methods, the cloth is first charged
with diamond paste of the specified size, and
then the appropriate lubricant is added. During
the polishing cycle, diamond of the same size is
added periodically in suspension form to keep
the cutting rate high. Comp stands for comple-
mentary and means that the head (specimen
holder) and base (platen) are both rotating in the
same direction, counterclockwise (usually).
Contra means that the head is rotating clockwise
while the base is rotating counterclockwise.
Contra is more aggressive than complementary.

Fig. 6 AISI W2 (1.05% C), spheroidize annealed. (a) Etched with boiling alkaline sodium picrate for 60 s to color the cementite brown. (b) Etched lightly with 4% picral and tint
etched with Beraha’s Na2S2O3/K2S2O5 reagent to color the ferrite (wide range of colors). (c) Etched lightly with 4% picral and tint etched with Beraha’s Na2MoO4 reagent to
color the cementite dark orange. 1000⳯

Fig. 7 AISI D2 austenitized at 1040
C (1900
F), air quenched, and tempered at 200
C (400
F). Influence of etchant on revealing martensite. (a) 10% nital etch reveals grain
boundaries, carbides, and martensite (light). (b) 4% picral plus HCl etch reveals carbides and martensite (light). (c) Heat tinted at 540
C (1000
F) for 5 min after 10% nital
etch to produce greater contrast and reveal the retained austenite. (d) Superpicral etch reveals retained austenite as white, but carbide also appears white. 1000⳯

If the head rotates at less than 100 rpm, the slur-
ries stay on the surface reasonably well. How-
ever, if the head rotational speed is greater than
100 rpm, the abrasive will be thrown off the
platen onto the user and the walls. In comple-
mentary mode, the centrifugal force throws the
abrasive off the platen surface and down the
drain. Therefore, the amount of abrasive that
must be added during a cycle depends on the
surface being used, the head speed, and the ro-
tational directions. When grinding, especially
with cast polymeric mounts, complementary ro-
tation may produce chatter and vibration, which
is eliminated when using contra rotation. In cer-
tain specimens that have very hard or very soft
(relative to the matrix) particles that are poorly
bonded to the matrix, one may see excessive re-
lief around these particles after the last step. If
this happens, and it is specimen-specific and not
frequent, simply repeat the last step in comple-
mentary rotation, and this problem will be elim-
inated.
Microetching. The etchant most widely used
for tool steels is 2 to 5% nital. Stock solutions
exceeding 3% HNO3 in ethanol should not be
stored in pressure-tight bottles. If higher concen-
trations are desired as a stock reagent, a bottle
with a pressure-relief valve should be used.
Methanol also may be substituted for ethanol,
although methanol poses health risks and thus
may not be recommended. (See the article “Lab-
oratory Safety in Metallography” in this vol-
ume.)
Nital is generally used for tool steels regard-
less of the anticipated microstructural constitu-
ents. Although nital is superior to picral (4% pi-
cric acid in ethanol) for etching martensitic
structures, picral produces better results for ex-
amining annealed samples. When examining
spheroidize-annealed tool steels (the most com-
mon annealed condition), picral reveals only the
Fig. 8 AISI W1 (1% C) overaustenitized at 925
C (1700
F) and water quenched, producing martensite, retained austenite, and small patches of pearlite. Influence of etchant on
revealing quenched martensite. (a) 2% nital etch reveals martensite and pearlite (black). (b) 4% picral etch reveals pearlite but only faintly reveals martensite. (c) 5% aqueous
sodium metabisulfite etch produces a strong contrast between the martensite and retained austenite (white). (d) Beraha’s Na2S2O3/K2S2O5 reagent produces similar results to (c), but
pearlite is more visible. 500⳯
Metallographic Techniques for Tool Steels / 649
interfaces between carbide and ferrite. Nital also
reveals the ferrite grain boundaries that generally
obscure the carbide shape. Also, because nital is
orientation sensitive, carbides within some of the
ferrite grains will be poorly delineated, making
spheroidization ratings more difficult. Figures
5(a) and (b) illustrate the difference in etching
response between nital and picral with spheroid-
ize-annealed W2 tool steel. Note that within
some grains, nital did not clearly reveal the ce-
mentite.
A 2% nital solution is usually preferred.
Stronger concentrations increase the speed of
etching, making it more difficult to control. Etch-
ing of martensitic high-alloy tool steels, such as
the high-speed steels, may require a 5 or 10%
concentration solution. Mix this solution fresh
using ethanol; do not store the solution in a
tightly stoppered bottle. Etching with nital or pi-
cral is usually performed by immersion. If swab-
bing is used, pressures should be light. Etching
times are difficult to generalize because of the
wide range of tool steel compositions and be-
cause heat treatment can markedly alter etch re-
sponse. Trial and error will determine the degree
of surface dulling necessary to obtain the correct
degree of etching.
Other etchants, although less frequently used,
can be of great value. Table 4 lists compositions
of a number of specialized reagents for achieving
selective etching or enhancing contrast among
microconstituents. As examples of the use of
various etchants, Fig. 5(c) and 6 show the same
W2 specimen as in Fig. 5(a) and (b) but etched
with four alternate reagents to evaluate the
spheroidized cementite. Figure 7 shows the mi-
crostructure of D2 tool steel, in the quenched and
tempered condition, revealed using three differ-
ent etchants and by heat tinting, while Fig. 8
demonstrates the effect of four different etchants
used to examine the structure of an improperly
heat treated specimen of W1 (1% C) water-hard-
ening tool steel.
Pepperhoff interference film technique
also improves contrast among constituents. A
thin layer of a dielectric compound, such as zinc
selenide (ZnSe), is vapor deposited onto the sur-
face of the sample in a bell jar (Ref 5). As the
thickness of this layer increases above 400 nm,
colors are observed (Ref 12). First-order red to
violet produces the best results. An example of
this method, and a comparison to a standard
etchant, is given in Fig. 9.
Prior-Austenite Grain Size. Many tool steels
can be etched with nital to reveal the prior-aus-
tenite grain boundaries. The high-speed steels
and the D-type cold work tool steels (Fig. 7) can
be handled in this way as long as the tempering
temperature used is not too high. Etching tech-
niques that reveal the prior-austenite grain
boundaries are employed but can be difficult to
implement successfully; therefore, a fracture
grain size method is widely used. The Shepherd
fracture grain size technique is simple, quick,
and accurate, as long as the sample is marten-
sitic—retained austenite may be present in sub-
stantial amounts—and not tempered to such an
extent that reasonably flat, brittle (macroscopic)
fractures cannot be obtained (Ref 5).
Microstructures of Tool Steels
A wide range of microstructures is observed
in tool steels because of variations in composi-
tion and heat treatment. The mill metallurgist is
generally most concerned with annealed micro-
structures and undesired surface decarburization.
The failure analyst sees a broad spectrum of mi-
crostructures, both normal and abnormal.
Hot-Worked Microstructures. The structure
produced after hot working can have a marked
650 / Metallography and Microstructures of Ferrous Alloys
influence on the distribution and morphology of
carbides after the subsequent spheroidize anneal.
The micrographs in Fig. 10 to 17 illustrate the
complex microstructures that are often present
in the as-hot-worked condition prior to annealing
and the influence of this structure on the an-
nealed microstructure. In general, the cooling af-
ter hot working must be controlled to produce as
uniform a carbon distribution as possible, so that
the annealed carbide distribution does not vary.
Some tool steels, such as the 5% Cr hot work
grades and the 12% Cr plastic molding steels,
tend to form carbide networks at the prior-aus-
tenite grain boundaries present at the end of the
hot working operation. Such networks can be
difficult to remove during annealing and can de-
grade tensile ductility and toughness, even if
they are semicontinuous. Figure 18 illustrates
grain-boundary carbide networks in type 420
stainless steel used for plastic molding. The
Fig. 9 AISI D2, quenched and tempered. Use of vapor-
deposited zinc selenide to accentuate carbide
detection and retained austenite. Samples were etched first
with 4% picral plus HCl (a) to outline the carbides, then
coated with a thin layer of zinc selenide (b) to reveal the
carbides (dark violet), retained austenite (white), and mar-
tensite (dark). 1000⳯
high-carbon, water-hardening grades may de-
velop grain-boundary carbide networks after
cooling from the hot rolling temperature, as
shown in Fig. 19. Stringers of complex alloy car-
bides may be observed in certain grades, and
these are often harmful. Figure 20 shows an ex-
ample in H13 tool steel.
Annealed Microstructures. Because most
tool steels are relatively hard, even when an-
nealed, it is usually necessary to control carbide
morphology during annealing to maximize
machinability and formability. For most tool
steels, a spheroidal carbide shape is the desired
condition, although for a few of the low-alloy
tool steels, certain machining operations are im-
proved when the structure is partially pearlitic.
Most tool steels and all high-alloy grades are
spheroidize annealed at the mill. Control of an-
Fig. 10 AISI W1 (1.3% C), as-rolled, containing pearl-
ite and acicular cementite. 4% picral. 500⳯
Fig. 12 AISI S4, as-rolled, containing ferrite (white) and
pearlite. 4% picral. 500⳯
nealed microstructures is discussed in the article
“Introduction to Heat Treating of Tool Steels” in
Heat Treating, Volume 4 of Metals Handbook,
9th ed. (1981). For a given grade, the hardness
decreases as the degree of spheroidization in-
creases. Once spheroidization has been obtained,
growth of the carbides, which produces fewer
carbides per unit volume and a greater apparent
spacing, further reduces hardness. However, if
the carbide structure is too coarse, dissolving the
required amount of carbon during austenitization
will be more difficult. In addition, many tool
steels require a fine, uniform distribution of un-
dissolved carbides to resist grain growth during
austenitization.
Control of the spheroidization annealing pro-
cess is important for good machinability and
good formability, such as in hobbing. The more
Fig. 11 AISI L6, as-rolled, containing bainite and mar-
tensite (white). 2% nital. 500⳯
Fig. 13 AISI S4, as-rolled, containing bainite and mar-
tensite (featureless patches). This bar was
cooled at a faster rate after rolling than the one in Fig. 12.
4% picral. 500⳯

uniform the starting microstructure (the as-rolled
microstructure), the more uniform the spheroid-
ization and the softer the annealed hardness, all
other conditions being the same. The as-rolled
microstructures shown in Fig. 10 to 17 demon-
strate varying degrees of non-uniformity and
variability in the starting microstructure. Figure
21 shows the influence of the starting micro-
structure on the spheroidization of W1 tool steel.
The as-rolled pearlite (Fig. 21a) is coarser in in-
terlamellar spacing than the normalized speci-
men (Fig. 21c), and the annealed structure, al-
though similar, is lower in hardness, with larger,
more widely spaced carbides for the normalized
and annealed specimen than for the as-rolled and
annealed specimen. Of course, if the specimen
contained grain-boundary carbide networks after
rolling, they would still be present after spher-
Fig. 14 AISI S5, as-rolled, containing bainite and mar-
tensite (white). 2% nital. 500⳯
Fig. 16 AISI L1, as-rolled, containing pearlite and a grain-boundary cementite net-
work. Boiling alkaline sodium picrate. 100⳯
Metallographic Techniques for Tool Steels / 651
oidize annealing, unless it was normalized be-
fore annealing. Figures 22 to 36 illustrate the
wide range of annealed microstructures that can
be observed in a variety of tool steel grades.
Carbides in Tool Steels. The amount and
type of carbides present depend on the bulk car-
bon content and the quantity of carbide-forming
elements (chromium, molybdenum, vanadium,
and tungsten, for example) in the grade. Ce-
mentite is present in the carbon and low-alloy
grades; more complex carbide types are found in
the highly alloyed grades. The hardness of car-
bides varies with their composition, from ap-
proximately 800 HV for pure Fe3C to approxi-
mately 1400 HV when other elements, such as
chromium, are substituted for a portion of the
iron. The high wear resistance of heat treated
tool steels is attributable to the hardness of the
Fig. 15 AISI O1, as-rolled, containing bainite and mar-
tensite (white patches). The dark patches are
pearlite. 4% picral. 500⳯
Fig. 17 AISI A2, as-rolled, containing plate martensite (black) and retained austenite
(white). 2% nital. 500⳯
matrix phase, chiefly martensite, and the amount
and type of carbides remaining undissolved in
the matrix.
Cementite (M3C) is an iron-rich carbide with
an orthorhombic crystal structure. In annealed
tool steels, it will be very low in tungsten, mo-
lybdenum, or vanadium content and relatively
low in chromium content, while the manganese
content can be high. Cementite is found in all
carbon tool steels and in alloy tool steels
quenched and tempered below 538
C (1000
F).
M7C3 is a chromium-rich carbide with a hexag-
onal crystal structure that is observed in steels
with medium-to-high chromium contents and
only moderate amounts of other carbide-forming
alloy elements. It dissolves very slowly in aus-
tenite during the hardening process. This carbide
is present in the D-type cold work grades in high-
speed steels in the annealed or highly tempered
conditions. M23C6 is a chromium-rich carbide
with a face-centered cubic (fcc) crystal structure
with a high solubility for iron, but much less for
other strong carbide formers, such as molybde-
num or tungsten. It is observed in type 420 stain-
less steel and in annealed high-speed steels. Fig-
ure 37 shows a portion of the isothermal section
of the Fe-Cr-C system at 870
C (1600
F), il-
lustrating the location of the various chromium-
rich carbides observed in several chromium-
bearing tool steels.
M6C is either a molybdenum- or a tungsten-
rich carbide with a fcc crystal structure, such as
Fe4Mo2C-Fe3Mo3C. A fair amount of chromium
or vanadium can be present in the carbide. It is
commonly seen in high-speed steels and dis-
solves slowly during austenization. Figure 38
shows an isothermal section in the Fe-W-C sys-
tem at 1200
C (2190
F), illustrating the loca-
tion of M6C carbides and the composition of sev-
eral hot work die steels. M2C is a molybdenum-
or tungsten-rich carbide with a hexagonal crystal
structure. It is not frequently seen in tool steels,
except for certain grades in the annealed condi-
652 / Metallography and Microstructures of Ferrous Alloys

Fig. 18 Grain-boundary carbide networks in type 420 martensitic stainless steel (Fe-0.35%C-0.4%Mn-13%Cr) with two different etchants. (a) Vilella’s reagent. (b) Beraha’s sulfamic
acid tint etch. Heat treatment: 1038
C (1900
F). Air quench: 177
C (350
F) temper. 500⳯

tion. MC is most frequently a vanadium-rich car- graphitization are not controlled. Processing pro- carbon hobbing steels, such as AISI P2, must be
bide with a fcc NaCl-type crystal structure. Other cedures can also affect graphitization; therefore, carburized after hobbing and before hardening.
strong carbide-forming elements, such as tita- in carbon tool steels with more than approxi- These low-carbon grades are rather soft as-an-
nium, niobium, tantalum, and zirconium, can mately 1.1% C, processing must also be care- nealed and are designed to minimize work hard-
form MC carbides, but these elements are not fully controlled. ening during forming. Medium-carbon AISI S5
common in tool steels. MC is observed in steels Sulfur is added to several tool steel grades to must be very carefully spheroidize annealed to
with moderate-to-high vanadium contents, improve machinability. Generally, the amount of as low a hardness as possible to enhance hobb-
chiefly high-speed tool steels. It has very strong sulfur added to tool steels is less than that added ability. Achieving a low annealed hardness with
bonds and is the hardest carbide. It resists dis- to free-machining carbon steels. Because man- this grade is difficult, however, because its high
solution during austenization. ganese sulfide inclusions degrade toughness, silicon content substantially strengthens the fer-
The amount of carbides present in tool steels certain tool steel grades are made with very low rite.
is greater in the annealed condition than after sulfur contents, often less than 0.003%, for criti- Heat Treated Microstructures. Tool steel
austenitizing and quenching, because the car- cal applications. Although this practice enhances compositions range from carbon tool steels with
bides supply the austenite with the carbon nec- mechanical properties, these tool steels can be no alloy additions to high-speed steels contain-
essary to achieve high hardness levels. The type more difficult to machine. ing 20% or more alloying elements. Conse-
of carbides obtained also varies as a function of Hobbing steels must be quite soft to permit quently, hardenabilities vary widely, producing
composition. As an example, Fig. 39 shows the optimal cold workability and maximum life of quenching requirements that vary from brine to
composition and amount of carbides observed in the master hob. Such steels are very low in car- air. Each tool steel grade has been studied to de-
different high-speed steels in the annealed and bon, although some medium-carbon alloy termine the proper quench media, as a function
in the hardened conditions. grades, such as AISI S5, are hobbed. The low-
Effect of Composition on Microstructure.
Because tool steels are somewhat more difficult
to machine than carbon and alloy steels, the com-
positions of some grades are adjusted by increas-
ing the silicon content to retain a certain amount
of the carbon present as graphite. When viewed
on a transverse plane (Fig. 40), the graphite ap-
pears as small, globular particles, but they are
not nodular in shape as in ductile cast iron. On
the longitudinal plane (Fig. 41), the graphite par-
ticles are shown to be elongated, although their
aspect ratios are not excessively high. The most
commonly used graphitic tool steel is AISI O6,
which typically contains approximately 0.3 to
0.5% of the total carbon content as graphite. The
amount of carbon as graphite must be controlled
carefully to ensure uniform hardening response.
The presence of graphite improves machining Fig. 19 Grain-boundary carbide networks after cooling
from the hot rolling temperature of high-car-
and wear characteristics.
Undesired graphitization can occur in high-
bon, water-hardening grade (Fe-1.31%C-0.35%Mn- Fig. 20 Carbides in light-etching segregation band of
0.25%Si, as-rolled). Alkaline sodium picrate etch: 90
C AISI H13 hot work die steel (Fe-0.40%C-
carbon tool steels if those elements that promote (195
F), 60 s. 500⳯ 0.8%Si-5.25%Cr-1%V-1.35%Mo). 2% nital. 500⳯
 Metallographic Techniques for Tool Steels / 653

of section size, to permit hardening to marten-
site. Although the carbon tool steels are usually
not through hardened, most of the other grades
are. Another exception is the low-carbon hob-
bing grades that are carburized and surface hard-
ened. Figure 42 shows the surface of a poorly
carburized specimen of P5 tool steel with an ex-
tensive intergranular carbide network and a car-
bide film on the surface. This mold failed pre-
maturely in service as a result. A few grades are
also nitrided or carbonitrided for special appli-
cations. Figure 43 shows the microstructure of
gas nitrided H13 tool steel, while Fig. 44 shows
an ion-nitrided H13 specimen. Note the (brittle)
white-etching iron nitride layer at the extreme
surface.
Most tool steels are hardened and tempered to
rather high hardnesses (generally, 58 HRC or
greater) to obtain good wear resistance. Excep-
tions are the hot work tool steels that are
quenched and tempered to hardnesses from ap-
proximately 42 to 55 HRC and prehardened plas-
tic molding steels, such as AISI P20, that are
sold in the heat treated condition at approxi-
mately 32 HRC. The prehardened tool steels are
machined and used in this condition without sub-
sequent heat treatment except, perhaps, for a
stress-relief temper.
The correct austenitizing temperature for each
grade has been determined experimentally by us-
ing an austenitizing series. Samples are heated
to various temperatures and quenched at a rate
consistent with the anticipated hardenability.
Each as-quenched sample is fractured to rate the
prior-austenite grain size by the Shepherd com-
parison method. Next, the samples are carefully
ground on one of the fracture faces and tested
for hardness. As the austenitizing temperature
increases, hardness will increase, level off, then
decrease. The fracture grain size will remain
relatively constant, usually up to the austenitiz-
ing temperature where the as-quenched hardness
levels out, then will decrease due to grain
growth. The optimal austenitizing temperature is
that temperature or range where the hardness is
highest and the grain size is finest. Dilatometry
is generally conducted before such tests to es-
tablish the optimal temperature range.
To illustrate the effect of varying the austeni-
tizing temperature on the microstructure of tool
steels, it is necessary to examine grades with
varying carbon content and carbide types. Figure
45 shows the microstructure of air-hardened S7
tool steel with a carbon content of approximately

Fig. 21 AISI W1 (1.05% C). Influence of starting structure on spheroidization. (a) As-rolled; contains coarse and fine pearlite. (b) After spheroidization (heat to 760
C, or 1400
F;
cool at a rate of 11
C/h, or 20
F/h, to 595
C, or 1100
F; air cool). (c) Austenitized at 870
C (1600
F) and oil quenched to produce fine pearlite. (d) Austenitized as in
(c); annealed as in (b). Note the more uniform spherical carbide shape compared to (b). 4% picral. 500⳯

Fig. 22 AISI W4 water-hardening tool steel (0.98C-
0.74Mn-0.14Cr-0.19Ni), as-received (mill an-
nealed). 187 HB. Spheroidal cementite in a matrix of fer-
rite; a considerable amount of lamellar pearlite is also
present. 4% picral. 1000⳯
Fig. 23 AISI W4 water-hardening tool steel (0.96C-
0.66Mn-0.23Cr), as-received (full annealed).
170 HB. Structure consists of spheroidal cementite in a fer-
rite matrix; no lamellar constituent is present. Compare
with Fig. 22. 4% picral. 1000⳯
Fig. 24 AISI W1 water-hardening tool steel (0.94C-
0.21Mn), as-received (mill annealed). 170 HB.
Structure: mixture of lamellar pearlite and spheroidal ce-
mentite in a matrix of ferrite, with a few large, globular
carbide particles. 3% nital. 1000⳯
654 / Metallography and Microstructures of Ferrous Alloys
0.5%. The preferred austenitizing temperature
for S7 is 940
C (1725
F), and the grade is rather
sensitive to under- and overaustenitization. Un-
deraustenitization does not dissolve enough car-
bide to get full hardness. Overaustenitization re-
sults in grain growth, because all of the carbide
is put in solution and it is not aluminum-killed,
so there is no AlN to inhibit grain growth. Figure
46 shows the microstructure of O1 tool steel, an
oil-hardening grade with approximately 0.9% C.
The preferred austenitizing temperature is 800

C (1475
F), so this series compares the correct
quenched microstructure to overaustenitized mi-
crostructures. It demonstrates how increasing the
carbon content of the austenite depresses the
martensite start temperature, resulting in increas-
Fig. 25 AISI L1, spheroidize annealed. Note the very-
well-formed spheroidal carbides. 4% picral.
500⳯
Fig. 28 AISI S7, spheroidize annealed. 4% picral.
1000⳯
ing retained austenite. A more dramatic effect on
the microstructure is observed when a high-car-
bon, high-alloy tool steel, such as type D2, is
examined in the overaustenitized condition. Fig-
ure 47 shows D2 after air quenching from vari-
ous temperatures, from 1010 to 1230
C (1850
to 2250
F). The recommended austenitizing
temperature is 1010
C (1850
F). Note that re-
tained austenite, which is present even at the cor-
rect austenitizing temperature, cannot be ob-
served by light microscopy until a substantial
amount is present; certainly, more than 10% is
required before it can be seen.
Carbon tool steels are hypereutectoid and con-
tain only cementite, which is easily dissolved.
The iron-carbon equilibrium diagram is a good
Fig. 26 AISI S2, spheroidize annealed. 4% picral.
1000⳯
Fig. 29 AISI A6, spheroidize annealed. 4% picral.
1000⳯
starting point for establishing the correct austen-
itizing temperature. For these steels, maximum
hardness results when approximately 0.60 to
0.65% C is put into solution. Therefore, the as-
quenched structure will consist of martensite and
residual cementite, that is, the carbides not put
into solution. A small amount of retained aus-
tenite will also be present, but it will not be de-
tectable with a light microscope if the proper
austenitizing temperature is used. Figure 48
shows the microstructure of W1 tool steel in the
hardened case, the transition zone, and the un-
hardened core after brine quenching a 19 mm
(0.75 in.) diameter bar. The case is high-carbon
martensite, and the core is very fine pearlite. Not
all of the cementite should be put into solution,
Fig. 27 AISI S5, spheroidize annealed. 4% picral.
500⳯
Fig. 30 AISI A6, partially spheroidized. Note lamellar
pearlite. 4% picral. 1000⳯

so residual cementite should be present at all lo-
cations. Quenched and tempered microstructures
of a variety of other low-alloy grades with me-
dium levels of carbon are shown in Fig. 49 to
54, while the microstructure of higher-alloy tool
steels are shown in Fig. 55 to 66.
If a sufficiently high austenitizing temperature
is used, the carbon content of the austenite will
be raised to such an extent that the martensite
finish temperature is well below room tempera-
ture. Because retained austenite is relatively soft
compared to martensite, the bulk hardness will
be lower. The microstructure will exhibit coarse
plate (acicular) martensite and retained austenite.
As the austenitizing temperature exceeds the op-
timal temperature, the amount of residual ce-
mentite decreases, the amount of retained aus-
tenite increases, the hardness decreases, and the
grain size increases.
Fig. 31 AISI H13 chromium hot-worked tool steel,
spheroidize annealed. 4% picral. 1000⳯
Fig. 34 AISI A10 tool steel, as-received (mill annealed).
Section transverse to rolling direction. At the
magnification used, the structure is poorly resolved. Nital.
100⳯
Metallographic Techniques for Tool Steels / 655
In general, if the amount of retained austenite
is high enough to be observed with a light mi-
croscope, the steel has been overaustenitized.
Tempering will not convert high levels of re-
tained austenite to martensite or bainite unless
the tempering temperature is rather high. More-
over, the retained austenite will not be stable
enough to withstand shock-induced transforma-
tion to martensite during service. When such
transformation occurs, the high-hardness matrix
lacks enough ductility to accommodate the trans-
formation stresses, and cracking results.
Low heat treated hardnesses may also result if
the section size and quench rate are selected in-
correctly for a particular grade. When the har-
denability is inadequate to permit full hardening,
pearlite or bainite will be observed in the micro-
structure. Ferrite may also be visible in the few
tool steels that are hypoeutectoid, although this
Fig. 32 AISI M2 molybdenum high-speed tool steel,
spheroidize annealed. 4% picral. 1000⳯
Fig. 35 AISI H23 tool steel, annealed by austenitizing
at 870
C (1600
F) for 2 h and cooling at 28

C/h (50
F/h) to 540
C (1000
F), then air cooling. 98 HRB.
Structure consists of tiny spheroidal and some larger alloy
carbide particles in a matrix of ferrite. Kalling’s reagent.
500⳯
is less common. Brine- and water-quenching
grades are also susceptible to formation of soft
spots within the case, caused by localized slow
cooling from tongs holding the sample or by in-
adequate agitation (failure to break up vapor
pockets due to localized boiling of the quench
media).
After quenching, tool steels must be immedi-
ately tempered to reduce the very high transfor-
mation stresses, or quench cracking may occur.
Quench cracking is more likely to occur as the
quench rate increases and if the geometry of the
specimen exhibits stress raisers. Air-hardenable
steels are less susceptible to quench cracking,
because the slow rate of cooling helps to relieve
some of the transformation stresses.
Many tool steels are often tempered at 175 to
230
C (350 to 450
F). These low tempering
temperatures do little to the structure except re-
Fig. 33 AISI A7 tool steel, box annealed at 900
C
(1650
F) for 1 h per 25 mm (1.0 in.) of con-
tainer thickness and cooled at no more than 28
C/h (50

F/h). Massive alloy carbide and spheroidal carbide in a
ferrite matrix. 4% nital. 1000⳯
Fig. 36 AISI H26 tool steel, annealed by austenitizing
at 900
C (1650
F), cooling at 8.5
C/h (15
F/
h) to 650
C (1200
F), then air cooling. 22 to 23 HRC.
Structure consists of a dispersion of fine particles of alloy
carbide in a matrix of ferrite. Picral with HCl, 10 s. 500⳯
656 / Metallography and Microstructures of Ferrous Alloys

Fig. 38 Isothermal section of Fe-W-C diagram at 1200

C (2190
F). Nominal compositions of tung-
sten, carbon, and iron for some tungsten hot work steels
are plotted. Source: Ref 8

cause secondary hardening and to change the na-

Fig. 37 Portion of the 870
C (1600
F) isothermal section of the Fe-Cr-C system with approximate compositions of
AISI H13, A2, D2, and type 420 steels indicated. Source: Ref 7
lieve quenching stresses. Hot work and high-
speed steels are usually tempered at relatively
high temperatures. Due to their high alloy con-
tent, these grades can resist softening during
tempering to rather high levels. These higher-
alloy steels are often tempered hot enough to
ture of the carbides present. These changes, how-
ever, can be detected only by methods more so-
phisticated than light microscopy. In general, the
lowest-alloy tool steels receive a single temper,
typically 2 h for every 25 mm (1 in.) of thick-
ness. Higher-alloy tool steels are usually tem-
pered twice; high-speed steels may be tempered
three times. Double and triple tempering is re-
quired to condition and stabilize the microstruc-
ture.
When a substantial amount of strong carbide-
forming elements are present, tempering at high
temperatures, where secondary hardening oc-
curs, results in a change in carbide composition
and type. To illustrate this, Fig. 67 shows the
effect of time and temperature on the type of
carbide present in a 12% Cr martensitic steel,
more highly alloyed than type 420. At low tem-
pering temperatures, M3C will be present. How-
ever, with higher temperatures and longer times,
M3C is replaced by M7C3 and M23C6, only the
latter being present at still higher temperatures
and longer times. This steel contained a some-
what high nitrogen content, and M2N nitrides

Fig. 39 Carbides in various high-speed steels, both in annealed conditions and after being heated to normal austen- Fig. 40 AISI O6, spheroidize annealed, transverse sec-
itizing temperatures. Open bars represent quantities in annealed steels. Solid bars indicate amounts after tion. Note the globular appearance of the
austenitizing at hardening temperatures indicated. graphite (black). 4% picral. 500⳯
 Metallographic Techniques for Tool Steels / 657

were observed as well. Figure 68 shows the se- carbide segregation and poor ingot-to-finished properties, tempers, designations, and applica-
quence of carbide formation in two tungsten- product yields. Consequently, the powder met- tions of tool steels can be found in the articles
type high-speed steels as a function of tempering allurgy process now makes many of these grades “Wrought Tool Steels” and “P/M Tool Steels” in
temperature. Both exhibit strong secondary routinely. Indeed, there are some grades that Properties and Selection: Irons, Steels, and
hardening at approximately 600
C (1110
F). have been developed that can only be made by High-Performance Alloys, Volume 1 of ASM
For many tool steels, tempering to approxi- powder metallurgy, and these grades exhibit out- Handbook (1990) and in Ref 11.
mately 540
C (1000
F) produces only subtle standing resistance to the high temperatures ex-
differences in the microstructure viewed opti- perienced by cutting tools. Figures 79 to 82 il-
cally, as shown in Fig. 69. The speed at which lustrate T15 high-speed steel made by powder
etching occurs and the darkness of the matrix metallurgy, showing the microstructure after hot
will change with tempering. Tempering just be- isostatic pressing, after it was spheroidize an-
low the lower critical temperature is required to nealed, and after it was hardened. The carbides
produce pronounced microstructural changes, are fine and evenly distributed, without any ap-
but such high tempers have no practical appli- parent segregation.
cations for tools and dies, except as an anneal. Compositions for the tool steels illustrated in
Heat treated tool steel microstructures are this article are listed in Table 5. Information on
similar in appearance when the grades are prop-
erly heat treated. The primary differences are the
amount and type of the residual, undissolved car-
bides that will influence the coarseness of the
plate martensite. In many tool steels, the marten-
site phase is so fine that little detail is observed.
This is not the case for grades that exhibit very
little residual carbides, for example, AISI S1, S5,
and S7. These shock-resisting tool steels have
lower carbon contents, and nearly all of the car-
bon is dissolved in the austenite. Consequently,
the martensite is coarser, with more detail ob-
servable by light microscopy.
In some cases, quenching does not produce a
fully martensitic structure. This occurs mainly
when the hardenability is inadequate for
through hardening for the section size and
quench medium chosen. The continuous cool- Fig. 42 Poorly carburized AISI P5 plastic-mold tool
steel with an extensive intergranular carbide
ing transformation (CCT) diagram is a good
tool for the metallurgist when evaluating heat
Fig. 41 AISI O6, spheroidize annealed, longitudinal network and a carbide film on the surface. Three steps with
section. Note that the graphite is elongated in a pressed synthetic chemical-textile pad; 10 min on step 3.
treatment problems. Unfortunately, diagrams do the rolling direction. 4% picral. 500⳯ Nital. 200⳯
not exist for all standard grades. Figure 70
shows a CCT diagram for S7 tool steel. Figures
71 and 72 illustrate the microstructural varia-
tions in S7 produced by varying the quench rate
from 2780 to 28
C/h (5000 to 50
F/h). Iso-
thermal transformation (IT) diagrams (also
called time-temperature-transformation or S-
curves) have often been used when diagnosing
heat treatment problems, but they cannot be
used with most tool steels, because the trans-
formations depicted by the IT diagram are much
different than those shown in the corresponding
CCT diagram. As an example, compare the
CCT diagram for S7 shown in Fig. 70 with the
IT diagram for S7 shown in Fig. 73. There is
some similarity here, but with higher-alloyed
tool steels, the similarity is less. The IT dia-
grams are very useful for developing annealing
cycles and for isothermal treatments such as
ausforming. Figure 74 shows the microstructure
of S7 held at 704
C (1300
F) for 30 min (only
a small amount of transformation before
quenching) and for 4 h (almost complete trans-
formation to pearlite). A wide range of isoth-
ermally formed microstructures is shown in Fig.
75 to 78 for S5 tool steel.
Powder Metallurgy Products. Highly al-
loyed grades, such as the high-speed steels, are
difficult to manufacture by ingot-making tech-
nology, because they are plagued by alloy and Fig. 43 Gas nitrided AISI H13 tool steel. Four steps with a rigid grinding disk. Nital. (a) 200⳯. (b) 1000⳯
658 / Metallography and Microstructures of Ferrous Alloys

Fig. 44 Ion nitrided AISI H13 tool steel with a brittle white-etching iron nitride layer at the extreme surface. (a) Mounted with silica-filled epoxy. (b) Nickel plated and mounted
with silica-filled epoxy. Vilella’s reagent. Note that in (b) the iron nitride layer may be easily missed due to the similar color of it on the plating. 1000⳯

Fig. 45 AISI S7 (0.5% C). Influence of austenitizing temperature. (a) Austenitized at 915
C (1675
F) 1 h for every 25 mm (1.0 in.) of thickness and air quenched. Sample is
underaustenitized. (b) Austenitized at 925
C (1700
F). Slightly underaustenitized. (c) Austenitized at the preferred temperature of 940
C (1725
F). (d) Austenitized at 955

C (1750
F). Slightly overaustenitized; note coarsening, no visible carbide. 4% picral. 500⳯

Fig. 46 AISI O1. Influence of austenitizing temperature on microstructure. (a) Austenitized at 800
C (1475
F) 1 h for every 25 mm (1.0 in.) of thickness. 65 HRC, grain size 9.5.
Specimen properly austenitized. (b) Austenitized at 870
C (1600
F). 65 HRC, grain size 9. Overaustenitized. (c) Austenitized at 980
C (1800
F). 64 HRC, grain size 7.
Very overaustenitized; all carbide dissolved. (d) Austenitized at 1100
C (2010
F). 64 HRC, grain size 3. Severely overaustenitized; note retained austenite (white). 4% picral. 500⳯
 Metallographic Techniques for Tool Steels / 659

Fig. 47 AISI D2 tool steel microstructure (Vilella’s etch, 1000⳯) after air quenching from various austenitizing tem-
peratures. Note that retained austenite, which is present even at the correct austenitizing temperature (1010

C, or 1850
F), cannot be observed by light microscopy until a substantial amount is present. (a) 1010
C (1850
F) air
quenched. (b) 1065
C (1950
F) air quenched. (c) 1120
C (2050
F) air quenched. (d) 1175
C (2150
F) air quenched.
(e) 1230
C (2250
F) air quenched
660 / Metallography and Microstructures of Ferrous Alloys

Fig. 48 AISI W1 (1.05% C), 19 mm (0.75 in.) diam bars, brine quenched. (a) Hardened case microstructure. 64 HRC. Case contains as-quenched martensite and undissolved
carbides. 4% picral. (b) 2% nital etch reveals martensite as dark rather than light. (c) Transition zone. 55 HRC. Martensite is light and undissolved, carbide is outlined, and
pearlite is dark. 4% picral. (d) Core microstructure. 42 to 44 HRC. 4% picral etch reveals fine pearlite matrix (black) containing some patches of martensite (white) and undissolved
carbides (outlined white particles). 1000⳯

Fig. 49 AISI S2, heated to 845
C (1550
F), water Fig. 50 AISI L6, heated to 840
C (1550
F), oil Fig. 51 AISI O2, heated to 850
C (1560
F), oil
quenched, and tempered at 150
C (300
F). quenched, and tempered at 150
C (300
F). 61 quenched, and tempered at 175
C (350
F). 61
59.5 HRC. Structure consists of martensite and some very HRC. Martensite and undissolved carbides are revealed. HRC. Martensite and a small amount of undissolved car-
fine undissolved carbide. 2% nital. 1000⳯ 2% nital. 1000⳯ bide are revealed. 2% nital. 1000⳯

Fig. 52 AISI S1, heated to 955
C (1750
F), oil
quenched, and tempered at 150
C (300
F). 58
to 59 HRC. Only martensite is visible. 2% nital. 500⳯
Fig. 55 AISI S7, heated to 940
C (1725
F), air
quenched, and tempered at 200
C (400
F). 58
HRC. Martensite and a small amount of undissolved car-
bides are observed. Vilella’s reagent. 1000⳯
Metallographic Techniques for Tool Steels / 661
Fig. 53 AISI S5, heated to 870
C (1600
F), oil
quenched, and tempered at 175
C (350
F). 60
HRC. Only martensite is visible. 2% nital. 1000⳯
Fig. 56 AISI S7, heated to 940
C (1725
F), air
quenched, and tempered at 495
C (925
F). 52
HRC. Martensite and a small amount of undissolved car-
bide are observed. Vilella’s reagent. 1000⳯
Fig. 58 AISI H11, heated to 1010
C (1850
F), air
quenched, and double tempered at 510
C
(950
F). 52 HRC. Martensite plus a small amount of very
fine carbide are visible. Vilella’s reagent. 1000⳯
Fig. 54 AISI P20, heated to 900
C (1650
F), water
quenched, and tempered at 525
C (975
F). 32
HRC. Matrix is martensite. Dark particles are manganese
sulfides. Contrast process orthochromatic film. 2% nital.
500⳯
Fig. 57 AISI A6, heated to 840
C (1550
F), air
quenched, and tempered at 150
C (300
F).
61.5 HRC. Martensite plus a small amount of undissolved
carbide are observed. 2% nital. 1000⳯
662 / Metallography and Microstructures of Ferrous Alloys

Fig. 59 AISI H13, heated to 1025
C (1875
F), air

quenched, and double tempered at 595
C
(1100
F). 42 HRC. All martensite plus a small amount of
very fine undissolved carbide. 2% nital. 1000⳯ Fig. 63 AISI M1, heated to 1175
C (2150
F), oil
quenched, and triple tempered at 480
C (900
Fig. 61 AISI D2, heated to 1010
C (1850
F), air
F). 62 HRC. Martensite plus undissolved carbide are re-
quenched, and tempered at 200
C (400
F). vealed. 2% nital. 1000⳯
59.5 HRC. Martensite plus substantial undissolved carbide;
note the prior-austenite grain boundaries. 2% nital. 1000⳯

Fig. 60 AISI H21, heated to 1200
C (2200
F), oil Fig. 62 AISI D3, heated to 980
C (1800
F), oil Fig. 64 AISI M2, heated to 1120
C (2050
F), oil
quenched, and tempered at 595
C (1100
F). quenched, and tempered at 200
C (400
F). quenched, and double tempered at 480
C
53.5 HRC. Martensite and undissolved carbide are ob- 60.5 HRC. Martensite plus substantial undissolved carbide (900
F). 62 HRC. Martensite plus undissolved carbide are
served. 2% nital/Vilella’s reagent. 1000⳯ are visible. 2% nital/Vilella’s reagent. 1000⳯ revealed. Vilella’s reagent. 1000⳯
 Metallographic Techniques for Tool Steels / 663

Fig. 65 AISI M4, heated to 1220
C (2225
F), oil Fig. 66 AISI M42, heated to 1175
C (2150
F), oil
quenched, and double tempered at 480
C quenched, and triple tempered at 565
C (1050
(900
F). 62 HRC. Martensite plus undissolved carbide are
F). 65 HRC. Martensite plus undissolved carbide are ob-
revealed. Vilella’s reagent. 1000⳯ served. Vilella’s reagent. 1000⳯

Fig. 67 Time-temperature diagram of carbides present

in two 12% Cr martensitic stainless steels after
tempering. Solid lines (for alloy A) and broken lines (for
alloy B) show when fine precipitates are first observed. Al-
loy A composition: 0.21% C, 13.2% Cr, and 0.24% N. Al-
loy B composition: 0.18% C, 0.58% Mn, 0.31% Si, 0.18%
Ni, 11.7% Cr, 0.49% Mo, 0.01% Al, 0.38% V, 0.20% Nb, Fig. 68 Sequence of alloy carbide formation in two
and 0.033% N. This diagram is based on observations of tungsten-type high-speed steels as a function of
specimens subjected to more than 30 different tempering tempering temperature. Steel A contains 0.8% C, 18% W,
treatments in the temperature interval of 500 to 700
C (930 4% Cr, 2% V, and 10% Co; steel B contains 0.8% C, 9%
to 1290
F). Source: Ref 9 W, 3% Cr, and 3% Co. Source: Ref 10
664 / Metallography and Microstructures of Ferrous Alloys

Fig. 69 Influence of tempering temperature on microstructure of AISI O1 (all: 4% picral, 500⳯). All specimens austenitized at 800
C (1475
F), oil quenched, and tempered at
different temperatures. (a) 200
C (400
F). 60 HRC. (b) 315
C (600
F). 55 HRC. (c) 425
C (800
F). 49 HRC. (d) 540
C (1000
F). 43 HRC

Fig. 70 Continuous coding transformation diagram for AISI S7 tool steel. Ms, martensite start; Mf, martensite finish;
Bs, bainite start; Bf, bainite finish; Ps, pearlite start; Pf, pearlite finish. Source: Atlas of Time-Temperature
Diagrams, ASM International
 Metallographic Techniques for Tool Steels / 665

Fig. 71 AISI S7 continuous cooling transformations. Some very fine undissolved carbide is present in all specimens in this series. (a) Austenitized at 940
C (1725
F) and cooled at
2780
C/h (5000
F/h). 62 HRC. Structure is martensite plus a small amount of bainite. (b) Cooled at 1390
C/h (2500
F/h) to produce a greater amount of bainite. 61.5
HRC. (c) Cooled at 830
C/h (1500
F/h). 56.5 HRC. Structure is mostly bainite plus some martensite (light). 4% picral. 500⳯

Fig. 72 AISI S7 continuous cooling transformations. Some very fine carbide is present in all specimens in this series. (a) Austenitized at 940
C (1725
F) and cooled at 445
C/h
(800
F/h). 51.5 HRC. Structure is nearly all bainite with some small patches of martensite (white). (b) Cooled at 220
C/h (400
F/h). 45 HRC. Structure is mostly bainite
with fine pearlite at the prior-austenite grain boundaries. (c) Cooled at 28
C/h (50
F/h) to 620
C (1150
F), then water quenched. Austenite present at 620
C (1150
F) was transformed
to martensite. Structure is mostly fine pearlite with patches of martensite (white). See also Fig. 71. 4% picral. 500⳯
666 / Metallography and Microstructures of Ferrous Alloys

Fig. 73 Isothermal transformation diagram for AISI S7 tool steel. Composition: 0.50% C, 0.71% Mn, 0.30% Si, 3.20%
Cr, and 1.32% Mo. Austenitized at 940
C (1725
F). Ms, martensite start; Bs bainite start; Bf, bainite finish; Ps,
pearlite start; Pf, pearlite finish. Source: Atlas of Time-Temperature Diagrams, ASM International

Fig. 74 Microstructure (picral etch, 500⳯) of AISI S7 tool steels with isothermal heat treatments. (a) Held at 704
C (1300
F) for 30 min (only a small amount of transformation
before quenching). (b) Held at 704
C (1300
F) for 4 h (almost complete transformation to pearlite)
 Metallographic Techniques for Tool Steels / 667

Fig. 75 AISI S5 austenitized and isothermally trans- Fig. 76 AISI S5 austenitized, isothermally transformed Fig. 77 AISI S5 austenitized, isothermally transformed
formed at 650
C (1200
F) for 4 h (air cooled) at 595
C (1100
F) for 8 h, and air cooled to (partially) at 540
C (1000
F) for 8 h, and water
to form ferrite and coarse pearlite. 23 to 24 HRC. 4% picral. form ferrite and fine pearlite. 36 HRC. 4% picral. 1000⳯ quenched to form upper bainite (dark); balance of austenite
1000⳯ formed martensite. 4% picral/2% nital. 1000⳯

Fig. 78 AISI S5 austenitized, isothermally transformed

at 400
C (750
F) for 1 h, and air cooled to Fig. 79 AISI T15, powder-made. Sample was slow Fig. 80 AISI T15, powder-made. Sample was hot isos-
form lower bainite. 37 to 38 HRC. 4% picral/2% nital. cooled after hot isostatic pressing. 28 HRC. tatically pressed, forged, and annealed. 24
1000⳯ Structure is partially annealed. 3% nital. 1000⳯ HRC. Structure is fully annealed. 3% nital. 1000⳯
668 / Metallography and Microstructures of Ferrous Alloys

Fig. 81 AISI T15, powder-made. Processed as in Fig.

80, then hardened; heated to 1230
C (2250
F) Fig. 82 AISI T15, powder-made. Same sample as in
for 5 min in salt, oil quenched, triple tempered 2 h each at Fig. 81 but etched in 100 mL H2O, 1 mL HCl,
540
C (1000
F). 65 HRC. 3% nital. 1000⳯ 1 g K2S2O5, and 1 g NH4•HF. 1000⳯

Table 5 Nominal compositions of illustrated tool steel grades

Composition, %
AISI
type C Mn(a) Si(b) Cr Ni V W Mo Co Ti
W1 0.6–1.4 ... ... ... ... 0.25 ... ... ... ...
W2 0.6–1.4 ... ... ... ... ... ... ... ... ...
S1 0.5 ... 0.75 1.5 ... 0.2(c) 2.5 ... ... ...
S2 0.5 0.4 1.0 ... ... ... ... 0.5 ... ...
S4 0.55 0.8 2.0 ... ... ... ... ... ... ...
S5 0.55 0.8 1.9 0.25(c) ... 0.2(c) ... 0.4 ... ...
S7 0.5 0.7 ... 3.25 ... ... ... 1.40 ... ...
O1 0.9 1.0 ... 0.5 ... 0.2(c) 0.5 ... ... ...
O2 0.9 1.6 ... ... ... ... ... ... ... ...
O6 1.45 0.8 1.1 ... ... ... ... 0.25 ... ...
A2 1.0 0.7 ... 5.25 ... 0.2(c) ... 1.1 ... ...
A6 0.7 2.0 ... 1.0 ... ... ... 1.35 ... ...
A7 2.00–2.85 0.8 0.5 5.0–5.75 0.3 3.9–5.15 0.5–1.5 0.90–1.40 ... ...
A10 1.25–1.50 1.6–2.1 1.0–1.5 ... 1.55–2.05 ... ... 1.25–1.75 ... ...
D2 1.5 0.5 ... 12.0 ... 0.2–0.9(c) ... 0.8 ... ...
D3 2.1 ... ... 12.0 0.5(c) ... ... ... ... ...
H11 0.35 ... 0.9 5.0 ... 0.4 ... 1.5 ... ...
H13 0.35 ... 1.0 5.25 ... 1.0 ... 1.3 ... ...
H21 0.35 ... ... 3.5 ... 0.4(c) 9.0 ... ... ...
H23 0.25–0.35 0.15–0.40 0.15–0.60 11.0–12.75 0.3 0.75–1.25 11.0–12.75 ... ... ...
H26 0.45–0.55 0.15–0.40 0.15–0.40 3.75–4.5 0.3 0.75–1.25 17.25–19.0 ... ... ...
T1 0.7 ... ... 4.0 ... 1.0 18.0 ... ... ...
T15 1.5 ... ... 4.0 ... 5.0 12.0 ... 5.0 ...
M1 0.8 ... ... 4.0 ... 1.1 1.5 8.5 ... ...
M2 0.85 ... ... 4.0 ... 2.0 6.0 5.0 ... ...
M4 1.3 ... ... 4.5 ... 4.0 5.5 4.5 ... ...
M42 1.1 ... ... 3.75 ... 1.15 1.5 9.5 8.0 ...
L1 1.0 ... ... 1.4 ... ... ... ... ... ...
L6 0.75 0.75 ... 0.9 1.75 ... ... 0.35 ... ...
F2 1.25 0.75 ... ... ... ... 0.35 ... ... ...
P5 0.1 ... ... 2.25 ... ... ... ... ... ...
P20 0.35 ... ... 1.25 ... ... ... 0.4 ... ...
AHT 1.0 ... ... 3.0 ... 0.25 1.05 1.1 ... 1.0
(a) All tool steels contain some manganese, generally 0.2–0.4% when not listed. (b) Tool steels usually contain 0.2–0.35% Si unless listed otherwise.
(c) Optional addition at discretion of manufacturer

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