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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.
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.
Table III. Mechanical Properties and Austenite Grain Sizes of C-Mn-B Plates (Tempering Temperature 5 593 7C)
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
Fig. 6—The CVN absorbed energy at 240 7C as a function of the Ti/N toughness generally decreases with increasing Ti/N ratio,
ratio of Q & T, 12.7-mm plates. as shown in Figures 6 and 7. Presumably, a portion of the
toughness reduction can be explained by an increase in the
cept for the lowest Ti/N ratio steel, all the plates appear to volume fraction of coarse TiN particles with increasing
be through hardened; at this thickness, the best B harden- Ti/N ratio. Also, in steels with excess Ti, some additional
ability factor is not needed. The tempering behavior of sev- loss of toughness could come from the precipitation of
eral of these as-quenched structures was also examined. Ti-rich particles on tempering. Consequently, in the high-
Figure 4 shows the midthickness hardnesses as a function N steels, the best toughness is observed in the low Ti/N
of tempering temperature. The hardness of all plates de- ratio steels. However, the toughness of the higher Ti/N ratio
creases continuously with increasing tempering temperature steels is significantly improved by reducing the N level
over the entire range evaluated (482 7C to 704 7C). At all (note the data for the low-N steels in Figures 6 and 7). Even
temperatures, steel TiN09 has lower hardness levels than with a hyperstoichiometric Ti/N ratio, steel TiN36-LN ex-
other plates, consistent with the lack of through hardening hibits a toughness level similar to that obtained in steels
on quenching (Figure 3). A small secondary hardening ef- TiN13 and TiN18 (Figure 7).
fect is observed in the higher Ti/N ratio steels (e.g., TiN37 The changes in tensile and impact properties are not the
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
(a) 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]
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 erage CVN absorbed energy of 40 J at 240 7C should be
ratio. In contrast, it is more appropriate to use the Ti/N ratio achievable for this C-Mn-B steel.
to explain the B-hardenability effect, and the effects of ex-
cess Ti (or excess N) on mechanical properties. G. Electron Microscopy Analysis of Fine Precipitates
The average CVN energy at 240 7C of the 12.7-mm
fully martensitic, Q & T plates is plotted against the (Ti)(N) The fine precipitates present in the Q & T condition for
product for these steels in Figure 10. (Note that the data steels TiN23 and TiN46 were analyzed using aluminum
for steel TiN09 are excluded since this steel did not through extraction replicas. Figure 11(a) shows the microstructure
harden on quenching.) The data band shows that in these at a junction of four prior austenite grains in steel TiN23.
tempered martensitic structures, toughness is inversely pro- Many particles are observed on the prior austenite grain and
portional to the (Ti)(N) product; i.e., toughness decreases martensitic lath boundaries, as well as within the grains.
as the volume fraction of coarse TiN particles increases. The size and location of these particles suggest they are
The beneficial effect of reducing both the Ti and N levels cementite, as typically found in tempered martensitic
on toughness can be further illustrated by comparing the steels.[17] At a higher magnification (Figure 11(b)), a large
results for steels TiN36-LN and TiN37. These steels have rectangular particle and some smaller square particles (in-
similar Ti/N ratios, and therefore exhibit comparable har- dicated by arrows) are identified as TiN, based on STEM
denability (Table II) and strength (Table III). However, by microanalysis.
reducing the (Ti)(N) product from 0.000275 wt pct2 (steel As discussed previously, steels with hyperstoichiometric
TiN37) to 0.00012 wt pct2 (steel TiN36-LN), the CVN en- Ti/N ratios have excess Ti, which is available for precipi-
ergy is significantly improved (from 34 to 46 J). Based on tation on tempering. The fine precipitates present in an ex-
the results shown in Figure 10, it appears that if the (Ti)(N) traction replica prepared from steel TiN46 are shown in
product is maintained below about 0.00015 wt pct2, an av- Figure 12(a). These particles are roughly spherical, with 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.