Effect of the Ti/N Ratio on the Hardenability and Mechanical

Properties of a Quenched-and-Tempered C-Mn-B Steel

YULIN SHEN and STEVEN S. HANSEN

Ten experimental 0.18 pct C-1.2 pct Mn- 0.002 pct B steels with various Ti/N ratios were evaluated
in this study. The hardenability of these steels was first determined using Jominy tests. Slab sections
were then rolled to produce 12.5-mm-thick plates, and subsequently quenched and tempered for
mechanical property evaluation. The volume fraction of coarse (greater than 1 mm) TiN particles
was measured in all steels using quantitative metallographic techniques. Scanning transmission elec-
tron microscopy was used to investigate fine precipitates, and scanning electron microscopy was used
to examine the fracture surface of Charpy specimens. The results show that a complete boron (B)
hardenability effect is obtained with Ti/N ratios ≥2.9, a value slightly below the stoichiometric Ti/N
ratio of 3.4. Any excess Ti, above that which combines with N, provides an additional increase in
hardenability on quenching (effect of Ti in solution) and an increase in strength on tempering (Ti
(C,N) precipitation). Steels with a higher (Ti)(N) product develop a higher volume fraction of coarse
TiN particles during solidification. These coarse TiN particles result in reduced toughness levels of
the heat-treated plates evaluated in the present study.

I. INTRODUCTION ing. In contrast, the extremely stable TiN particles remain

IN quenched-and-tempered (Q & T) low and medium
carbon steel, a small amount of boron (B) is commonly
added to provide the required hardenability at minimum
alloy cost. In these B-treated grades, solute B segregates to
the grain boundaries during austenitizing and, thereby, re-
tards the ferrite transformation on quenching.[1] However,
if there is any dissolved nitrogen available, boron nitride
(BN) readily forms due to the relatively high B diffusivity
and the stability of BN in austenite. These BN particles
remain largely undissolved at normal austenitizing temper-
atures (e.g., around 900 7C),[1,2] resulting in a significant
reduction in, or loss of, the B-hardenability effect. To main-
tain the desired B-hardenability effect, strong nitride-form-
ing elements, such as Ti, Al, Zr, and even B (at high levels),
can be added to combine with the available nitrogen in
B-treated steels.[1,3–5] The most stable nitride is ZrN, fol-
lowed by TiN, AlN, and BN. However, Kapadia et al.[3]
have shown that a Zr addition does not provide effective B
protection. It has also been found that the excess B ap-
proach results in decreased hardenability (the coarse iron-
borocarbide particles act as nucleation sites) and tough-
ness.[6] Consequently, additions of Ti or Al are the two
primary methods currently used for B-protection in Q & T
steels.
When using Ti to protect B, common steelmaking prac-
tice is to add at least the stoichiometric amount of Ti (i.e.,
aiming for a Ti/N ratio ≥3.4) to precipitate any available N
before the B addition. Because TiN is thermodynamically
more stable than BN, TiN forms in preference to BN at
high temperatures. In Ti-protected steels, some of the B
may be present as iron-borocarbides after hot rolling. These
borocarbides readily dissolve during subsequent austenitiz-
YULIN SHEN, Research Engineer, and STEVEN S. HANSEN,
Manager, are with Homer Research Laboratories, Bethlehem Steel
Corporation, Bethlehem, PA 18016-7699.
Manuscript submitted June 18, 1996.
virtually undissolved during austenitizing, keeping nitrogen
out of solution and preventing BN formation.[3] However,
while Ti is very effective in ‘‘protecting’’ the B, coarse
TiN particles have been reported to initiate cleavage frac-
ture in both ferritic[7] and martensitic[8] steels. If coarse TiN
particles do have an adverse effect on toughness, the
amount of Ti added to B-alloyed steels should be limited
to the levels required to ensure a complete B-hardenability
effect.
The present study examines the effect of Ti/N ratio on
the hardenability and mechanical properties of a low C-Mn-
B steel. Laboratory heats with various Ti and N levels will
be evaluated.
II. EXPERIMENTAL PROCEDURE
Ten experimental heats were melted in a laboratory vac-
uum induction furnace and cast as 227 kg, 216-mm square
by 508-mm long ingots. These as-cast ingots were then re-
heated at 1260 7C and rolled to 100 3 125-mm (cross-
sectional) billets. Small samples were cut from these billets
and rolled to produce 38-mm-thick plates. Jominy bars
were machined from these plates and used to assess the
hardenability of the steels following the procedures speci-
fied in ASTM A255-89, ‘‘Standard Method for End-
Quench Test for Hardenability of Steel’’.[9] The Jominy bars
were austenitized at 927 7C for 30 minutes in a controlled
endothermic atmosphere (consisting of 41.4 vol pct H2,
36.6 pct N2, 19.6 pct CO, and 1.3 pct CH4) to minimize
scaling and decarburization. After testing, two flat and par-
allel surfaces were ground on each specimen, and the Rock-
well C hardness was measured in increments of 1.59 mm
(1/16 in.) from the quenched end. These Jominy hardnesses
were then used to calculate ideal diameters, DI, based on
the 50 pct martensite hardnesses tabulated in ASTM A255-
89. To delineate the prior austenite grains in the Jominy
specimens, a modified Winsteard’s solution (20-g picric
acid, 100-mL ethyl alcohol, 2000-mL water, and 50-mL

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 28A, OCTOBER 1997—2027

 Table I. Product Analyses of the Experimental Steels (Weight Percent)

Steel C Mn P S S Ni Cr
TiN09 0.19 1.20 0.019 0.014 0.23 0.010 ,0.01
TiN13 0.18 1.17 0.014 0.016 0.24 0.016 0.020
TiN18 0.19 1.16 0.014 0.015 0.25 0.017 0.019
TiN23 0.18 1.18 0.015 0.017 0.24 ,0.01 0.018
TiN25 0.17 1.20 0.016 0.016 0.25 0.014 0.018
TiN32 0.18 1.19 0.016 0.016 0.24 0.017 0.019
TiN37 0.19 1.19 0.016 0.016 0.25 0.016 0.018
TiN46 0.18 1.20 0.016 0.017 0.24 0.018 0.020
TiN36-LN 0.18 1.17 0.016 0.015 0.25 0.020 0.019
TiN52-LN 0.17 1.16 0.016 0.016 0.25 0.020 0.019

Ti/N
Steel Cu Al B Ti N Ratio Tiex* Nex**
TiN09 0.016 0.052 0.0015 0.010 0.0107 0.93 — 0.0078
TiN13 0.019 0.047 0.0021 0.009 0.0070 1.29 — 0.0044
TiN18 0.022 0.049 0.0023 0.016 0.0088 1.82 — 0.0041
TiN23 0.019 0.051 0.0021 0.016 0.0069 2.32 — 0.0022
TiN25 0.021 0.053 0.0021 0.020 0.0080 2.50 — 0.0022
TiN32 0.022 0.056 0.0022 0.025 0.0078 3.21 — 0.0005
TiN37 0.021 0.051 0.0023 0.032 0.0086 3.72 0.0026 —
TiN46 0.023 0.051 0.0022 0.039 0.0085 4.59 0.0099 —
TiN36-LN 0.018 0.047 0.0018 0.021 0.0058 3.62 0.0012 —
TiN52-LN 0.041 0.046 0.0016 0.030 0.0058 5.17 0.0102 —
*Tiex 5 total Ti 2 3.42 N.
**Nex 5 total N 2 Ti/3.42.

sodium tridecylbenzene sulfonate) was used for etching.

The austenite grain size was measured near the quenched
end using the three-concentric-circle intercept counting pro-
cedure described in ASTM E112-88, ‘‘Standard Methods
for Determining Average Grain Size.’’[10]
Subsequently, additional billet samples were reheated at
1260 7C and rolled to produce 12.7-mm-thick plates for
further evaluation. All as-rolled plates were austenitized at
927 7C for 30 minutes and quenched in water. The as-
quenched hardness was measured through the thickness for
each plate, and the tempering behavior (hardness at the
plate midthickness location) was evaluated over the tem-
perature range of 482 7C to 704 7C. For mechanical prop-
erty evaluation, all the as-quenched plates were tempered
at 593 7C for 30 minutes and air cooled. The austenite grain
size of these as-tempered plates was measured using the
procedure described previously. Transverse tensile proper-
ties were evaluated using standard ASTM 9-mm-diameter
specimens (tested in duplicate). Charpy V-notch (CVN)
transition curves were developed (including triplicate test-
ing at 240 7C) using transverse full-size Charpy specimens.
The fracture surfaces of selected broken Charpy specimens
were investigated using an Amray 1600 scanning electron
microscope (SEM). The volume fraction of coarse TiN par- Fig. 1—Jominy curves for the experimental C-Mn-B steels. The specimens
ticles was measured on as-polished specimens following the were austenitized at 927 7C for 30 min (at temperature) prior to end
procedure specified in JIS G 0555 (1977), ‘‘Microscopic quenching.
Testing Method for Non-Metallic Inclusions in Steel’’,[11]
with a 400-point grid and a magnification of 400 times in average edge length of TiN particles was measured at a
65 fields. In the present study, ‘‘coarse’’ TiN particles were magnification of 1000 times.
taken to have edge dimensions ≥1 mm, the minimum size Analytical electron microscopy of extraction replicas was
resolvable in an optical microscope. In addition to the vol- conducted to analyze fine precipitates (2 to 100 nm in di-
ume fraction determination, the total number of coarse TiN ameter). The replication procedure started with metallo-
particles observed in these 65 fields was recorded, and the graphically polishing the specimens and pre-etching in a 2

2028—VOLUME 28A, OCTOBER 1997 METALLURGICAL AND MATERIALS TRANSACTIONS A

 Table II. Results of Jominy Testing, Austenitizing Condition: 927 7C for 30 Minutes

DI calc, excluding B DI calc, excluding B Austenite

Ti/N J50 pct M* DI measured (GS 7) (GS corrected) B Grain Size ASTM
Steel Ratio (mm) (mm) (mm) (mm) Factor** (mm) Number
TiN09 0.93 3.8 28.2 15.3 14.5 1.84 22.4 7.7
TiN13 1.29 4.9 35.6 14.9 14.0 2.39 21.1 7.8
TiN18 1.82 4.2 31.0 15.7 15.4 1.97 25.1 7.3
TiN23 2.32 6.5 45.5 14.9 14.4 3.05 24.8 7.4
TiN25 2.50 4.6 34.0 14.4 13.7 2.36 22.6 7.6
TiN32 3.21 6.7 46.2 15.1 15.2 3.06 29.2 6.9
TiN37 3.72 7.3 50.0 16.0 15.4 3.13 24.0 7.5
TiN46 4.59 8.2 55.1 15.3 15.0 3.60 26.1 7.2
TiN36-LN 3.62 6.9 47.5 15.0 13.4 3.17 17.2 8.4
TiN52-LN 5.17 8.1 54.9 14.2 12.5 3.87 16.3 8.6
*J50 pct M 5 Jominy distance for 50 vol pct martensite, based on the tabulated 50 pct martensite hardnesses provided in ASTM A255-89.
**B factor 5 DI measured/DI calc (excluding B, GS 7).

pct nital solution. A thin Al film (about 30-nm thick) was

then evaporated onto the etched specimens in a vacuum
evaporator equipped with a cryogenic pump (to avoid car-
bon contamination). The Al film with embedded fine pre-
cipitates was then scribed into 3-mm squares and separated
from the specimen surface by etching in a 10 pct nital so-
lution. Finally, the replicas were floated off in distilled wa-
ter and collected on Al grids. The replicas were initially
examined in a PHILIPS* EM300 transmission electron mi-
*PHILIPS is a trademark of Philips Electronic Instruments Corp.,
Mahwah, NJ.

croscope (TEM) operating at 100 kV. If the quality of spec-

imens was satisfactory, the compositions of the fine precip-
itates were determined in a VG Scientific HB501 scanning
transmission electron microscope (STEM). Equipped with
a field emission gun, the HB501 STEM has a probe size of
1 nm when operating at 100 kV with a beam current of 1
nA; a windowless X-ray detector provides high sensitivity
for the analysis of light elements.

III. RESULTS AND DISCUSSION

A. Steel Composition
Table I shows the product analyses of the ten experi-
mental steels investigated in this study. With a nominal
base composition of 0.18C-1.2Mn-0.002B, these steels con-
tain various combinations of Ti and N and can be divided
into two groups based on N content: (1) high-N steels with
N levels in the range of 70 to 100 ppm and (2) low-N steels
with N levels of about 60 ppm. The combinations of dif-
ferent Ti (range of about 0.01 to 0.04 wt pct) and N levels
result in Ti/N ratios that vary from 0.93 to 5.17. In this
article, each steel is referred to by the ‘‘rounded-off’’ Ti/N
ratio. For example, steels TiN09 and TiN46 have Ti/N ra-
tios of 0.93 and 4.59, respectively. The LN designation
used in Table I for steels TiN36-LN and TiN52-LN refers
to ‘‘low nitrogen.’’ Note that steels TiN37, TiN46,
TiN36-LN, and TiN52-LN all have hyperstoichiometric
Ti/N ratios; these steels have ‘‘excess Ti’’ after all the
available N is precipitated as TiN. The calculated excess Ti
or excess N levels for all the steels are shown in Table I.
Fig. 2—BFs as a function of the Ti/N ratio for the experimental C-Mn-B
steels.
B. Hardenability
Figure 1 shows Jominy curves for the experimental steels
(these data are also summarized in Table II). In general,
the hardenability increases with increasing Ti/N ratio, in-
dependent of N level. The effectiveness of the various Ti
additions can be derived from these curves by an evaluation
of the B-hardenability effect, expressed as a boron factor
(BF). Here, the BF is obtained by dividing the measured
hardenability (the effect of all alloying elements, including
B) by the calculated base hardenability excluding B (using
the multiplying alloy factors provided in ASTM A255-89).
Separate DI calculations were done for (1) a constant aus-
tenite grain size of ASTM 7, following ASTM A255-89
procedures; and (2) the measured grain sizes (range of
ASTM 6.9 to 8.6) using the grain size correction developed
by Grossman.[12] A comparison of these calculations (Table
II) shows that the grain size correction has only a modest

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 28A, OCTOBER 1997—2029


Fig. 3—As-quenched through-thickness hardness profiles of experimental
12.7-mm, C-Mn-B plates. The plates were austenitized at 927 7C for 30
min (at temperature) and water quenched.
effect on the base hardenability. In addition, it has been
suggested that the effect of grain size on hardenability in
B-treated steels is not as significant as in B-free steels, since
B inhibits the grain boundary nucleation of ferrite.[1] As a
result, the small grain size differences observed in this
study are not expected to have a significant effect on sub-
sequent comparisons. Consequently, the DI values for a
constant grain size of ASTM No. 7 were used in the BF
calculations (Table II).
The higher the BF, the greater the contribution of B to
hardenability and, hence, the more effective is the protec-
tion provided by the Ti addition. Figure 2 shows the cal-
culated BFs as a function of Ti/N ratio (note that the low-N
and high-N results are comparable). Overall, the data define
a band where the BF increases with increasing Ti/N ratio.
This data band consists of three distinct regimes.
(1) For Ti/N ratios up to about 2.5, the BF is low and
inconsistent, suggesting incomplete protection of the B
by Ti.
(2) All steels with Ti/N ratios ≥2.9 have good BF; this
Fig. 4—Tempering curves (midthickness hardness vs tempering
temperature) for the 12.7-mm plates. Tempering times were 30 min (at
temperature).
means that in these steels, the BF is fully protected by
Ti.
(3) At Ti/N ratios above about 3.4, the BF starts to increase
again. In this regime, the BF probably include a har-
denability contribution from some of the excess Ti in
the steel (present as TiC) that dissolves during austen-
itizing.[13,14]
On the basis of these results, a ‘‘threshold’’ point for com-
plete B protection can be defined at a Ti/N ratio of 2.9 (the
point that separates regimes I and II). The data of Kapadia
et al.[3] on low-C, Ni-Cr-Mo steels and those of Nakasato
and Takahashi[4] on low-C, Mn steels also suggest that a
Ti/N ratio ≥2.9 provides full B protection, consistent with
the present results. Note that a Ti/N ratio of 2.9 is below
the stoichiometric Ti/N ratio of 3.4 commonly used in the
alloy design of B-alloyed Q & T grades.
C. As-Quenched Hardness and Tempering Behavior
The through-thickness hardness profiles of the as-
quenched, 12.7-mm-thick plates are shown in Figure 3. Ex-

Table III. Mechanical Properties and Austenite Grain Sizes of C-Mn-B Plates (Tempering Temperature 5 593 7C)

0.2 Pct Yield Tensile Reduction Austenite

Strength Strength Elongation in Area Charpy Energy Grain Size ASTM
Steel (MPa) (MPa) (Pct) (Pct) at 240 7C (J) (mm) Number
TiN09 605 689 22.5 57.5 52 17.7 8.4
TiN13 607 691 21.0 56.6 45 19.8 8.0
TiN18 614 701 21.0 57.6 47 20.9 7.9
TiN23 611 700 20.5 56.8 42 21.0 7.9
TiN25 608 693 21.0 57.3 41 24.0 7.5
TiN32 620 705 20.5 56.4 35 22.0 7.7
TiN37 642 719 19.5 55.2 34 21.2 7.8
TiN46 669 737 19.3 55.9 30 20.1 8.0
TiN36-LN 646 724 22.0 61.1 46 19.5 8.1
TiN52-LN 697 763 20.0 58.6 32 17.4 8.4

2030—VOLUME 28A, OCTOBER 1997 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 5—Yield and tensile strengths as a function of the Ti/N ratio of Q
& T, 12.7-mm plates.
Fig. 6—The CVN absorbed energy at 240 7C as a function of the Ti/N
ratio of Q & T, 12.7-mm plates.
cept for the lowest Ti/N ratio steel, all the plates appear to
be through hardened; at this thickness, the best B harden-
ability factor is not needed. The tempering behavior of sev-
eral of these as-quenched structures was also examined.
Figure 4 shows the midthickness hardnesses as a function
of tempering temperature. The hardness of all plates de-
creases continuously with increasing tempering temperature
over the entire range evaluated (482 7C to 704 7C). At all
temperatures, steel TiN09 has lower hardness levels than
other plates, consistent with the lack of through hardening
on quenching (Figure 3). A small secondary hardening ef-
fect is observed in the higher Ti/N ratio steels (e.g., TiN37
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 7—Charpy energy transition curves for the Q & T, 12.7-mm plates.
and TiN46) in the temperature range of 593 7C to 649 7C,
presumably due to the precipitation of fine titanium car-
bides.
D. Mechanical Properties
The mechanical properties of the Q & T 12.7-mm plates
are shown in Table III. Most of the plates exhibit through
hardening (Figure 3), which is indicative of a uniform, fully
martensitic microstructure through the entire plate thick-
ness. Consequently, since all steels have similar carbon lev-
els, the strength levels of these plates are expected to be
comparable. This is clearly the case for steels with Ti/N
ratios less than about 3.0, as shown in Figure 5. However,
at higher Ti/N ratios (i.e., in the steels containing excess
Ti), the strength increases continuously with increasing
Ti/N ratio. This strength increment at the higher Ti/N ratios
is probably due to fine Ti-rich precipitates formed on tem-
pering. Consistent with this strength increase, the tensile
ductility (both elongation and reduction in area) of these
12.7-mm plates decreases slightly with increasing Ti/N ra-
tio, for Ti/N ratios above 3.0.
Independent of changes in strength level, the CVN
toughness generally decreases with increasing Ti/N ratio,
as shown in Figures 6 and 7. Presumably, a portion of the
toughness reduction can be explained by an increase in the
volume fraction of coarse TiN particles with increasing
Ti/N ratio. Also, in steels with excess Ti, some additional
loss of toughness could come from the precipitation of
Ti-rich particles on tempering. Consequently, in the high-
N steels, the best toughness is observed in the low Ti/N
ratio steels. However, the toughness of the higher Ti/N ratio
steels is significantly improved by reducing the N level
(note the data for the low-N steels in Figures 6 and 7). Even
with a hyperstoichiometric Ti/N ratio, steel TiN36-LN ex-
hibits a toughness level similar to that obtained in steels
TiN13 and TiN18 (Figure 7).
The changes in tensile and impact properties are not the
VOLUME 28A, OCTOBER 1997—2031

(a)
(b)
(c)
Fig. 8—Fracture surfaces of Charpy specimens of (a) TiN23, showing
MnS and TiN inside the dimple fractures; (b) TiN46, showing TiN
particles inside large dimples; and (c) TiN46, showing a coarse TiN
particle in the path of brittle fracture.
result of variations in austenite grain size. As shown in
Table III, the austenite grain size is nearly constant (range
of ASTM 7.5 to 8.4) for all steels. With this small differ-
ence in grain size, the discussion of mechanical properties
2032—VOLUME 28A, OCTOBER 1997
will be primarily focused on the effects of the Ti and N
levels in the steels evaluated.
E. SEM Fractography
The role of coarse TiN particles on toughness was in-
vestigated by examination of the fracture surfaces of broken
Charpy specimens (tested at 240 7C) from plates TiN23
and TiN46. The sample from steel TiN23 exhibits predom-
inantly ductile fracture, while that from steel TiN46 shows
about 50 pct shear fracture. In the fully ductile fracture
region of the TiN23 sample, both MnS inclusions and
coarse TiN particles (about 5 to 10 mm in size) are observed
inside the dimples (Figure 8(a)). This suggests that coarse
TiN particles act like MnS inclusions; both types of parti-
cles provide initiation sites for ductile fracture, presumably
by decohesion of the inclusion/steel interfaces.[15] Similar
ductile fracture behavior is observed in the sample from
steel TiN46. For example, Figure 8(b) shows that coarse
TiN particles are responsible for the large dimples found
on sample TiN46. On the other hand, the role of coarse
TiN particles in brittle fracture is less clear. Figure 8(c)
shows a coarse TiN particle in the path of a brittle fracture
in a Charpy sample from steel TiN46 (tested at 2101 7C).
This TiN particle does not contribute to the initiation of the
cleavage fracture. In our fractography studies, we could find
no evidence of TiN particles initiating brittle fracture, in
contrast to an earlier report in the literature.[8]
F. Quantitative Metallography—Coarse TiN Particles
The tendency to form coarse TiN particles during solid-
ification increases as the product of the steel Ti and N con-
tents increases. The higher the (Ti)(N) product, the higher
the supersaturation at a given temperature, and the greater
the driving force for precipitation of TiN particles. At a
constant temperature, the (Ti)(N) solubility product is fixed.
In steels with (Ti)(N) products above this solubility limit,
there is a potential for TiN precipitation. During solidifi-
cation, high levels of Ti and N are expected in the inter-
dendritic liquid due to microsegregation. The (Ti)(N) prod-
uct in these interdendritic regions could exceed the
solubility limit of TiN in liquid steel, leading to the precip-
itation of TiN.[16] At these high temperatures, the TiN par-
ticles can grow rapidly, resulting in coarse TiN particles in
the interdendritic regions of as-cast structures. These coarse
TiN particles eventually become somewhat dispersed dur-
ing the ingot breakdown and plate hot rolling steps. Assum-
ing that the degree of solute enrichment during
solidification is proportional to the bulk solute content,
steels TiN37 and TiN46 would be expected to have the
highest volume fraction of coarse TiN particles. In contrast,
steels TiN09 and TiN13 have the smallest (Ti)(N) products
and should, therefore, have the fewest coarse TiN particles.
The volume fraction of coarse TiN particles in each 12.7-
mm plate was measured by optical microscopy techniques.
These data, along with information on particle size and
number, are provided in Table IV. Note that the average
TiN particle size is similar in all the steels. As shown in
Figure 9, the volume fraction of coarse TiN particles in-
creases proportionally with the (Ti)(N) product, a result in
good agreement with the trends discussed previously.
Therefore, any effects related to coarse TiN particles should
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table IV. Quantitative Metallography—Coarse TiN Particles

Average Edge
(Ti)(N) Vol Pct of Number of Length of TiN
1024 3 Coarse TiN Coarse TiN Particles
Steel Ti, Wt Pct N, Wt Pct Wt Pct2 Particles Particles (mm)
TiN09 0.010 0.0107 1.07 0.00384 8 4.69
TiN13 0.009 0.0070 0.63 0 8 3.31
TiN18 0.016 0.0088 1.41 0.01538 32 4.51
TiN23 0.016 0.0069 1.10 0.00769 18 4.75
TiN25 0.020 0.0080 1.60 0.01153 38 3.28
TiN32 0.025 0.0078 1.95 0.02307 91 4.75
TiN37 0.032 0.0086 2.75 0.04230 92 5.38
TiN46 0.039 0.0085 3.32 0.04230 120 4.62
TiN36-LN 0.021 0.0058 1.20 0.01602 100 not measured
TiN52-LN 0.030 0.0058 1.74 0.02212 134 not measured

Fig. 9—The volume fraction of coarse TiN particles measured in the Q Fig. 10—The CVN absorbed energy at 240 7C in the Q & T, 12.7-mm
& T, 12.7-mm plates as a function of the corresponding (Ti)(N) product. plates as a function of the (Ti)(N) product.

be analyzed using the (Ti)(N) product instead of the Ti/N
ratio. In contrast, it is more appropriate to use the Ti/N ratio
to explain the B-hardenability effect, and the effects of ex-
cess Ti (or excess N) on mechanical properties.
The average CVN energy at 240 7C of the 12.7-mm
fully martensitic, Q & T plates is plotted against the (Ti)(N)
product for these steels in Figure 10. (Note that the data
for steel TiN09 are excluded since this steel did not through
harden on quenching.) The data band shows that in these
tempered martensitic structures, toughness is inversely pro-
portional to the (Ti)(N) product; i.e., toughness decreases
as the volume fraction of coarse TiN particles increases.
The beneficial effect of reducing both the Ti and N levels
on toughness can be further illustrated by comparing the
results for steels TiN36-LN and TiN37. These steels have
similar Ti/N ratios, and therefore exhibit comparable har-
denability (Table II) and strength (Table III). However, by
reducing the (Ti)(N) product from 0.000275 wt pct2 (steel
TiN37) to 0.00012 wt pct2 (steel TiN36-LN), the CVN en-
ergy is significantly improved (from 34 to 46 J). Based on
the results shown in Figure 10, it appears that if the (Ti)(N)
product is maintained below about 0.00015 wt pct2, an av-
erage CVN absorbed energy of 40 J at 240 7C should be
achievable for this C-Mn-B steel.
G. Electron Microscopy Analysis of Fine Precipitates
The fine precipitates present in the Q & T condition for
steels TiN23 and TiN46 were analyzed using aluminum
extraction replicas. Figure 11(a) shows the microstructure
at a junction of four prior austenite grains in steel TiN23.
Many particles are observed on the prior austenite grain and
martensitic lath boundaries, as well as within the grains.
The size and location of these particles suggest they are
cementite, as typically found in tempered martensitic
steels.[17] At a higher magnification (Figure 11(b)), a large
rectangular particle and some smaller square particles (in-
dicated by arrows) are identified as TiN, based on STEM
microanalysis.
As discussed previously, steels with hyperstoichiometric
Ti/N ratios have excess Ti, which is available for precipi-
tation on tempering. The fine precipitates present in an ex-
traction replica prepared from steel TiN46 are shown in
Figure 12(a). These particles are roughly spherical, with a

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 28A, OCTOBER 1997—2033

 (a) (a)

(b)
(b)
Fig. 11—TEM micrographs from an extraction replica specimen of steel
TiN23 showing (a) an area consisting of four prior austenite grains and
(b) TiN particles.

diameter in the range of 5 to 10 nm. The chemical com-

positions of these precipitates were examined using STEM
microanalysis. Figure 12(b) shows the annular dark-field
image for a small area in steel TiN46, where several fine
precipitates (bright spots) are indicated by arrows. The
compositions of these particles are all very similar. A typ-
ical X-ray spectrum (for particle C in Figure 12(b)) is
shown in Figure 12(c). In this spectrum, the Al and O sig-
nals (from the replica substrate) have been subtracted using
a spectrum acquired from a nearby precipitate-free area.
The presence of the Ti, C, and N (overlaps the Ti L-line)
signals suggests that this small spherical particle is a
Ti(C,N) precipitate. Although the amount of C and N could
not be quantitatively determined, since most of the N has
been precipitated earlier as TiN, it is likely that these par-
ticles are C rich. The presence of some N in these precip-
itates may be the result of the mutual solubility of TiC and
TiN, as reported for carbides and nitrides in most microal-
loying systems.[16,18–21] This observation confirms the con- (c)
tribution of excess Ti to the small strength increment
Fig. 12—(a) TEM micrograph of an aluminum extraction replica for steel
observed in the higher Ti/N ratio steels. TiN46 showing fine precipitates; (b) annular dark-field micrograph of fine
This study has shown that a Ti/N ratio of about 2.9 en- Ti(C,N) precipitates; and (c) X-ray microanalysis for particle C, which is
sures full protection of the B-hardenability effect in a indicated by an arrow in (b).

2034—VOLUME 28A, OCTOBER 1997 METALLURGICAL AND MATERIALS TRANSACTIONS A

0.18C-1.2Mn-0.002B steel. Any excess Ti, above that re-
quired to combine with the available N as TiN, presumably
precipitates as Ti carbonitrides in the as-rolled plate. During
subsequent austenitizing, some of these particles dissolve,
and the solute Ti contributes to hardenability on quenching.
Subsequently, this dissolved Ti reprecipitates as fine
Ti(C,N) particles during tempering, thereby providing a
modest strength increment.
A high (Ti)(N) product promotes the formation of rela-
tively coarse TiN particles (≥1 mm) during solidification.
These coarse nitrides have a negative effect on toughness.
Consequently, a reduced (Ti)(N) product is desired for op-
timum toughness. This can be achieved by reducing both
the Ti and N levels, while maintaining a minimum Ti/N
ratio to ensure adequate hardenability. For the C-Mn-B
steel considered in the present study, it appears that the best
combination of hardenability, strength, and toughness can
be obtained if the following two conditions are satisfied.
(1) There is a minimum Ti/N ratio ≥2.9 to achieve the full
B-hardenability effect.
(2) The Ti and N levels are restricted to keep the (Ti)(N)
product as low as possible. For example, if the N level
is limited to 50 ppm, a Ti melt range of 0.015 to 0.025
wt pct would be sufficient to maintain adequate har-
denability. This would provide a (Ti)(N) product in the
range of 0.000075 to 0.000125 wt pct2.
IV. CONCLUSIONS
The key findings of the present investigation can be sum-
marized as follows.
1. Complete protection of the B-hardenability effect in a
0.18C-1.2Mn-0.002B steel is obtained with Ti/N ratios
≥2.9; this ratio is slightly below the stoichiometric Ti/N
ratio of 3.4.
2. Excess Ti (above that required to combine with N) pro-
vides an increase in hardenability on quenching and a
strength increase on tempering due to the precipitation
of fine Ti(C,N) particles.
3. There is a linear relationship between the volume frac-
tion of coarse (≥1 mm) TiN particles and the (Ti)(N)
product. The higher the steel’s (Ti)(N) product, the more
coarse TiN particles are formed during solidification.
4. Coarse TiN particles act as inclusions to reduce tough-
ness in the ductile fracture regime. The toughness of Q
METALLURGICAL AND MATERIALS TRANSACTIONS A
& T plates generally decreases as the volume fraction
of coarse TiN particles increases.
ACKNOWLEDGMENTS
The authors thank H.B. Leuckel, R.R. Lichty, J.C. Hlu-
bik, R.E. Steigerwalt, R.J. August, S.J. Lawrence, L.L.
Hahn, K.E. Downey, W. Furdanowicz, and G.F. Cartwright
for their assistance in the experimental work and in the
preparation of this article.
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