ASM Handbook, Volume 4D, Heat Treating of Irons and Steels
J. Dossett and G.E. Totten, editors
DOI: 10.31399/asm.hb.v04d.a0005963
Heat Treating of Boron Steels
Anjana Deva and Bimal Kumar Jha, Steel Authority of India
ALTHOUGH THE POTENTIAL EFFECT
of small additions of boron on the hardenability
of steels has been known for over seventy years
(Ref 1–4), the steel industry has been slow to
fully exploit the use of this element. The impor-
tance of boron does not lie only in its economic
advantages, but more specifically, in the con-
tinuing improvement in the understanding of
its behavior and the development of controls
and practices that assure consistent and uniform
response from boron additions.
The advantage of boron—the extremely small
amount necessary for a significant hardenability
effect—is also its primary disadvantage: the
high degree of control required in steelmaking
necessitated by the sensitivity of the steels to
very small variations in boron content. Basic
metallurgical work devoted over the last 30 years
to a better understanding of the metallurgy of
these steels has brought forth a level of under-
standing sufficient to alleviate the old distrust
toward boron steels. Modern steelmaking
practices now allow the production of boron
steels of optimal boron content and consistent
hardenability.
It is not overly surprising to find a strong
renewed interest in boron steels, on the part of
both steelmakers and steel users, at a time when
the problem of material availability and cost is
second only to that of energy. Within the
framework of the development of high-strength
low-alloy (HSLA) steels, boron alloying should
therefore be envisioned as a potentially very
attractive route. Synergistic effects with other
alloying or microalloying elements, such as
niobium, should also be taken into serious con-
sideration for new energy-saving processes
such as direct quenching after the rolling mill.
Boron is useful as an alloying element in
many materials, but here it is illustrated as an
alloying element in steel because of its effect
on hardenability enhancement. Even quantities
of less than 100 ppm boron provide the same
effect on hardenability enhancement as other
more expensive elements that must be added
in much larger quantities. In recent times, the
effect of boron on hardenability has also been
studied through thermomechanical simulation.
This article discusses the effect of boron in heat
treated as well as thermomechanically simulated
steel.
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Hardenability of Boron Steel
Boron has aroused the interest of many materi-
als scientists with its hardenability-enhancing
effect when used as an alloying element in steels
(Ref 1–4). The effect of boron and the need to
control its location and chemical state have been
known since the 1940s (Ref 1). Early attempts at
commercial production of heat treatable steels
resulted in variable properties because of diffi-
culties in ensuring that boron was present in the
desired form, for example, soluble boron in the
case of steels in which boron is intended to
enhance hardenability. Subsequently, the impor-
tance of protecting boron using strong nitride
formers such as titanium was appreciated
(Ref 3). However, problems can be encountered
in obtaining a consistent effect, as can be seen
from the wider hardenability bands that are spe-
cified for boron-treated steels compared to their
chromium/molybdenum/nickel equivalents. On
the other hand, similar problems can be encoun-
tered in areas where an unprotected boron addi-
tion is made to modify other properties, for
example, ductility or formability in low-carbon
steels.
Boron Hardenability Mechanism. Boron
increases hardenability by retarding the trans-
formations to bainite, ferrite, and pearlite (each
of which is softer than martensite) that would
otherwise occur following annealing or hot
working as the steel cools down after austeniti-
zation (Ref 5). With the possibility of boron
concentration reaching significant levels, a
number of mechanisms for retarding ferrite
nucleation have been discussed by the authors
(Ref 6) with due consideration of reduction in
austenite grain-boundary energy, reduction in
diffusivity, reduction in number of sites, and
nucleation of ferrite on borocarbides. It was
concluded that the proposed boron hardenabil-
ity mechanisms are remarkably similar, except
for details of how the ferrite C-curve changes.
Their predictions regarding grain size, austeni-
tizing temperature, and borocarbide concentra-
tion are qualitatively the same. The reason is
that all the mechanisms depend directly or indi-
rectly on the concentration of boron absorbed in
the austenite grain boundaries during austenitiz-
ing. These theories predict that achieving the
Copyright # 2014 ASM InternationalW
All rights reserved
asminternational.org
maximum concentration of free boron (presum-
ably by avoiding boron interaction with oxygen
or nitrogen) is the key to optimizing the boron
effect.
Effect of Composition on Hardenability.
The boron hardenability effect is undoubtedly
affected by composition. During the last two
decades, the consensus has been that only a
small amount of dissolved boron is needed to
increase the hardenability of steel (Ref 7). The
suggested mechanism is based on the assump-
tion that boron in elemental form segregates at
the prior-austenite grain boundaries, suppres-
sing the ferrite reaction and thus improving
the hardenability. Thus, the effectiveness of
boron in increasing hardenability depends on
the form of boron retained in the steel. These
forms are influenced by the presence of other
elements such as oxygen, nitrogen, titanium,
and zirconium. Boron reacts with oxygen to
form B2O3, with nitrogen to form BN, and
with carbon to form iron borocarbide Fe23(CB)6
and iron borocementite Fe3(CB). The loss of
effective boron by the formation of B2O3 is
prevented by making the boron addition to
silicon-aluminum-killed steels and by using
good ladle and mold practices to avoid reoxida-
tion while pouring the steel. The loss of effec-
tive boron by formation of BN is prevented by
combining nitrogen with strong nitride formers.
To protect boron from nitrogen, titanium, a
potent nitride-forming element, is frequently
used. Titanium nitride (TiN) forms in the liquid
state prior to solidification and is a very stable
compound in the solid state. Hence, it does
not dissociate during heat treatments and, when
added in proper quantity, it efficiently blocks
nitrogen.
Kapadia et al. (Ref 8) have studied the influ-
ence of nitrogen, titanium, and zirconium on
the boron-induced hardenability of construc-
tional alloy steel and have brought out a physi-
cally meaningful correlation between the
observed hardenability effects of boron, as
described by:
 
Beff ¼ B  fðN  0:002Þ  Ti=5  Zr=15g0 0
In this equation, the chemical symbols repre-
sent the total weight percent of the respective
elements contained in the steel, and Beff is the
 180 / Heat Treating of Carbon and Low-Alloy Steels

effective boron participating in the enhance- Aim boron. %

ment of hardenability. According to this equa- 0 0.001 0.006
tion, the boron combined with nitrogen is No additive
152.4 (6.0) Titanium 3
equivalent to the weight percentage of nitrogen 6 Zirconium
available after combining with aluminum, sili- Nitrogen Numbers × 0.001%
con, and vanadium, which together account 7

Ideal diameter, mm (in.)

127.0 (5.0)
for a fixed amount of 0.002 wt% N. The result-

Multiplying factor
9
ing relationship between observed hardenability
and effective boron is shown in Fig. 1.
101.6 (4.0) 4 4 2
The maximum effect is obtained at a boron 7 5
content of approximately 0.001 to 0.003 wt%, 9
with an average value of approximately 0.0015%. 4
Boron content above the optimal amount tends 76.2 (3.0) 6
5 6
to promote the precipitation of boron-rich 7
9
grain-boundary constituent, which depletes the
austenite grain boundaries of boron atoms and 50.8 (2.0) 1
Base-metal hardenability
results in an overall loss of effectiveness, pro-
duces a reduction in the hardenability effect,
and can cause embrittlement and hot shortness. 25.4 (1.0)
Carbon is yet another element that has a pro- 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007
Effective boron (β), %
nounced effect on boron-induced hardenability
in steel. Figures 2 and 3 confirm that boron is
Fig. 1 Effect of effective boron content on hardenability of the steels. Source: Ref 8. Reprinted with permission of the
most effective in low-carbon steels in which Association for Iron & Steel Technology (AIST)
hardenability is controlled by the proeutectoid
ferrite reaction, and moreover that the effect is 0.5

Increase in hardenable diameter, mm

Increase in hardenable diameter, in.
more pronounced in fine-grained steels than in 12
coarse-grained steels. It has been shown Numbers denote
0.4 austenite grain 10
(Ref 1, 9) that the hardenability effect of boron size in ASTM
diminishes with increasing carbon content and 8
0.3 10
becomes almost negligible at the eutectoid
composition. On the influence of alloy content, 8 6
the best generalization that can be made is 0.2 6
that the greater the hardenability of the base 4 4
steel, the lower will be the hardenability effect 0.1
2
of boron. Boron is best used in low-carbon
steels with low alloy content. 0 0
The following results illustrate the general
0 0.2 0.4 0.6 0.8
relations between carbon content, the harden-
Carbon, %
ability of the base composition, and the boron
factor. Figure 4 shows that there is a definite Fig. 2 Hardenable diameter (90% martensite at center
as water-quenched) of Fe-0.5 Mn alloys with Fig. 3 Variation of hardenability effect of boron
trend for the boron factor to decrease as the base and without boron as a function of carbon content. with carbon content at various austenite grain
hardenability increases, but there is considerable Source: Ref 9. Reprinted with permission of the sizes in Fe-C-0.5 Mn alloys. Source: Ref 9. Reprinted
Association for Iron & Steel Technology (AIST) with permission of the Association for Iron & Steel
scatter in the results. Figure 5 shows that when Technology (AIST)
the boron factor is compared with carbon con-
tent, the steels separate into two groups, with all
carbon-manganese steels exhibiting a higher 3.4 3.4
boron factor than the other multiple-alloy steels SAE 15B16 SAE 15B16

(Ref 10). 2.6 41B30

2.6 15B30
Effect of Heat Treatment Parameters on DI(Jom) 15B30
15B35
41B25 DI(Jom) 15B35
Hardenability. Other factors influencing the DI(Chem) 41B30
15B48
86B30 41B16
41B25 DI(Chem)
effective level of boron present in the steel are 1.8 41B28 41B30 15B48
41B35 41B22
the austenitizing times and temperatures of prior 41B22 15B61 1.8
50B60 15B61
thermal treatment. These heat treating para- 86B30 86B45
1.0 41B35
meters influence the solution and precipitation 50B60
0 1 2 3 4 5
of boron carbides and, in the case of boron DI(Chem) 1.0
“fade,” nitrides within the grains or at the grain 0 0.2 0.4 0.6 0.8
boundaries. These are complex reactions that Carbon, %
Fig. 4 Relationship of boron factor to DI using
can be avoided by proper attention to heat corrected carbon factor. Source: Ref 10.
treating procedures, but they often account for Reprinted with permission of the Association for Iron & Fig. 5 Relationship of boron factor to carbon content
using corrected carbon factor. Source: Ref 10.
Steel Technology (AIST)
unexpected embrittlement or loss of the harden- Reprinted with permission of the Association for Iron &
ability effect when the steel is mistreated. Steel Technology (AIST)
The hardenability of boron steel is generally
said to decrease on heating above 1000  C case on austenite grain size, from ASTM 8-9
(1830  F). Boron steel must also be tempered at 875  C (1605  F) to ASTM 5-6 at 950  C (Ref 12–14). However, it is very clear that if
at a lower temperature than other alloy steels (1740  F) and ASTM 2-3 at 1100  C martensitic hardenability is considered, the
of the same hardenability. Hardenability in- (2010  F) (Ref 7, 11). The situation is different increase in hardenability due to grain size is
creases with austenitizing temperature in low- in cases where boron-nitrogen or more complex somewhat smaller in boron steels than in
nitrogen steels. Boron has little effect in this Al-B-N interactions need to be considered boron-free steels.

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 Heat Treating of Boron Steels / 181

In the optimal boron range of 10 to 30 ppm,
the largest boron effect is observed at low or
intermediate austenitizing temperatures (unless
the boron effect is reinforced by the high-
temperature dissolution of niobium). Boron
hardenability is retained, if not increased, for
cooling directly after hot rolling.
Heat Treatment of Boron Steel
As discussed in the preceding section, the
effect of boron on hardenability is entirely dif-
ferent in low- and high-carbon steel, unalloyed
and low-alloyed steel, with low and high soak-
ing temperature, and more significantly with
low and high cooling rate. These parameters
significantly influence the segregation and pre-
cipitation of boron and thereby the final
mechanical properties of the steel. A strong
dependence of cooling rate on effectiveness of
boron as hardener is observed.
Unalloyed Boron Steel. A study (Ref 15)
examined the hardening behavior of boron-free
and boron-added low-carbon steel in heat treat-
ment experiments by varying the austenitizing
temperatures and cooling conditions. These
parameters were found to influence signifi-
cantly the final mechanical properties of the
steel. Figure 6 depicts yield strength (YS) and
at 930  C. It is interesting to note that YS and (Ref 6, 16). The austenitizing temperature of
UTS for the boron-added steel are both substan- 890  C is close to the Ac3 temperature in the
tially higher for samples austenitized at 890  C present study, and based on the previous theory,
than at 930  C. the quantity of effective boron is greater at this
It is worth mentioning that in spite of the temperature than at 930  C. Transmission elec-
higher amount of boron in solution at 930  C, tron micrographs of steel in the OQ and WQ
YS and UTS reached their maximum values at states after austenitizing at 890  C (Fig. 7)
890  C in the WQ condition for boron-added clearly show the presence of martensitic laths
steel, although not much difference is observed in the WQ state indicating critical cooling con-
in these values for boron-free steel. This result dition somewhere in between OQ and WQ for
can be explained by the segregation of boron unalloyed boron added steel.
to the grain boundaries. Hardenability is domi- The previous study was carried out with low-
nated mainly by the grain-boundary concentra- carbon low-manganese unalloyed steel. How-
tion of boron atoms. It is established that ever, with increases in carbon and manganese,
when boron segregates to austenite grain the hardenability of boron steel increases consid-
boundaries, the austenite-to-ferrite transforma- erably, and a number of steel grades with rela-
tion is retarded; when it coagulates (or precipi- tively high carbon (0.2 to 0.4%) and manganese
tates), on the other hand, its retarding effect is (1.0 to 1.5%) have been used as quenchable
decreased. So the segregated boron is effective, boron steels. These grades are used in applica-
but the coagulated or precipitated boron is inef- tions requiring good wear-resistance properties.
fective in suppressing the transformation. Their extreme hardness after heat treatment
Hence, it is reasonable to define the boron that makes these grades particularly suitable for
has been segregated at austenite just before applications requiring high wear/abrasion re-
the transformation as “effective boron.” Fur- sistance. Their use allows significant weight
thermore, the effective boron content depends savings (up to 50% compared with an HSLA
on the thermal hysteresis in the austenite range grade) in structural and automotive components.
Effect on YS Effect on UTS
440 63.8 600 87.0
Boron-free steel 409 Boron-free steel 577

Tensile strength, MPa

Tensile strength, ksi

ultimate tensile strength (UTS) of low-carbon 557
Yield strength, MPa

Yield strength, ksi

400 Boron-added steel 58.0 540 Boron-added steel 78.3
389
aluminum-killed steels in boron-free versus
boron-added conditions (0.05% C, 0.2% Mn, 360 52.2 480 69.6
349 466
0.028% Si, 25 ppm B) heat treated with three 455
320 46.4 420 60.9
324
different austenitizing temperatures (850, 890,
and 930  C, or 1560, 1635, and 1705  F), fol- 280
259
40.6 360 337 52.2
252 325
lowed by three varying cooling rates: air cool- 240 34.8 300 43.5
ing (AC), oil quenching (OQ), and water AC OQ WQ AC OQ WQ
Cooling conditions Cooling conditions
quenching (WQ) (Ref 15). The YS values are
similar in the AC condition at 850  C (Fig. 6a). (a) Austenitizing temperature: 850 °C (d) Austenitizing temperature: 850 °C
In the OQ condition, there is less increase in 440 63.8 600 87.0
Boron-free steel Boron-free steel
YS for the boron-added steel as compared to 424 559
Tensile strength, MPa
Yield strength, MPa

Tensile strength, ksi

Yield strength, ksi

400 Boron-added steel 58.0 540 Boron-added steel 78.3

the boron-free steel. With a further increase in 385
354 494
cooling rate, as in the WQ case, the increase in 360 52.2 480 69.6
YS is greater for the boron-added steel than for 433
320 46.4 420 60.9
the boron-free steel. When the austenitizing tem- 307
394
perature is raised, the trend of increase in YS 280 40.6 360 52.2
249 336
with increase in cooling rate is found to be the 247 34.8 322
240
same as observed at 850  C. A dissimilarity is AC OQ WQ
300
AC OQ WQ
43.5

found with respect to the difference in YS value Cooling conditions Cooling conditions
for OQ versus WQ (Fig. 6b, c). With a further (b) Austenitizing temperature: 890 °C (e) Austenitizing temperature: 890 °C
increase in austenitizing temperature to 930  C,
the difference in YS value is found to be greater 440 63.8 600 87.0
Boron-free steel Boron-free steel
for OQ than for WQ (Fig. 6a–c).
Tensile strength, MPa
Yield strength, MPa

Yield strength, ksi

Tensile strength, ksi

400 Boron-added steel 402 58.0 540 Boron-added steel 78.3

For plots relating UTS values to increasing 381 522
cooling rate and austenitizing at 850, 890, and 360 52.2 480 485 69.6
342
930  C (Fig. 6d–f), the trend is similar to that
320 46.4 413
observed for YS. The UTS values are similar 302
420 60.9
for boron-free and boron-added steels when 280 40.6 385
256 360 52.2
cooling rate is very slow (AC) at all austenitiz- 247
330 338
240 34.8
ing temperatures. The increase is less in the AC OQ WQ 300 43.5
case of boron-added steel as compared to that AC OQ WQ
Cooling conditions
in boron-free steel for OQ at 890  C. With a Cooling conditions

further increase in cooling rate for WQ, the
increase in UTS is greater for boron-added steel
than for boron-free steel. The trend for both
steels with increase in cooling rate is similar
(c) Austenitizing temperature: 930 °C (f) Austenitizing temperature: 930 °C
Fig. 6 Effect of boron on yield strength (YS) and ultimate tensile strength (UTS) with varying cooling rate when
cooled from austenitizing temperature of (a and d) 850  C (1560  F), (b and e) 890  C (1635  F), and
(c and f) 930  C (1705  F). AC, air cooling; OQ, oil quenching; WC, water quenching

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 182 / Heat Treating of Carbon and Low-Alloy Steels

Table 1 Chemical composition of quenchable boron steel

Composition, %
Steel grade C Mn P S Si Al Ti B

22MnB5 AM FCE 0.200–0.250 1.10–1.40 0.025 0.008 0.15–0.35 0.015 0.020–0.050 0.0020–0.0050
30MnB5 AM FCE 0.270–0.330 1.15–1.45 0.025 0.005 0.17–0.35 0.015 0.020–0.050 0.0010–0.0050
30MnB5 EN 10083 0.270–0.330 1.15–1.45 0.025 0.035 0.17–0.35 ... ... 0.0010–0.0050
30MnB5 DRUM AM FCE 0.270–0.330 1.15–1.45 0.025 0.020 0.17–0.35 0.015 0.020–0.050 0.0010–0.0050
38MnB5 AM FCE 0.360–0.420 1.15–1.45 0.025 0.005 0.17–0.35 0.015 0.020–0.050 0.0010–0.0050

Weight loss, lmgl

500.00

S235JR
450.00

400.00 S355MC

350.00

30MnB5 DRUM AM FCE

300.00

250.00

200.00
100.00 120.00 140.00 160.00 180.00 200.00
Hardness, IHM

Fig. 8 Comparison of the abrasion resistance of untreated 30MnB5 AM FCE with standard structural grades (ASTM G
65 test procedure). Source: Ref 17

Jominy distance, in. Jominy distance, in.

0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 1.0
50 65

45
55
Fig. 7 (a) Bright-field image (magnification 8000X) 40
showing absence of martensitic laths at oil-
Hardness, HRC

Hardness, HRC

quenched state. (b) Bright-field image (8K) showing 45

presence of martensitic laths at water-quenched state 35

30
ArcelorMittal (Richfield, Ohio) (Ref 17) produces 35
the following quenchable boron grades: 22MnB5 25
AM FCE, 30MnB5 AM FCE, and 38MnB5 AM 25
FCE (Table 1). Theses grades are suitable for 20
water quenching, which makes the process more
environmentally friendly (less effluent treat- 15 15
0 5 10 15 20 0 5 10 15 20 25
ment) than that used for conventional carbon Jominy distance, mm Jominy distance, mm
steels. Their hardening performance is excellent (a) (b)
with both liquid and gas quenching. The main
applications for these steel grades after heat Fig. 9 Jominy curve of (a) 22MnB5 AM FCE and (b) 30MnB5 AM FCE. Source: Ref 17
treatment include agricultural machinery (discs,
plowshares), machinery for public works and
mining, and cutting equipment. Grade 30MnB5 The recommended austenitizing temperature The recommended austenitizing temperature of
DRUM AM FCE is a modified version of for 22MnB5 AM FCE is 880  C (1615  F). The 30MnB5 AM FCE is 830 to 850  C (1525 to
30MnB5 for applications such as concrete mix- temperature at the beginning of the quenching 1560  F). The temperature at the beginning of
ers, in which steel is used untreated. Abrasion process (i.e., at the maximum cooling rate) is the quenching process (i.e., at the maximum
tests (Fig. 8) show a good performance compared 750  C (1380  F). The Ac3 temperature is cooling rate) is 730  C (1345  F). These grades
with standard structural grades. The lower the 860  C (1580  F) for a heating rate of 5  C/s can be hot or cold formed. Typical mechanical
weight loss, the better is abrasion resistance; as (9  F/s), the Ac1 temperature is 750  C, and mar- properties of a 6 mm (0.2 in.) specimen in the
a result, parts have a longer lifetime. The Jominy tensite start temperature (Ms) is 400  C (750  F). rolling direction before and after quenching are
curves of both 22MnB5 AM FCE and 30MnB5 In a tensile test, after austenitization for 5 min at depicted in Table 2.
AM FCE (Fig. 9) give the hardness as a function 850  C (1560  F) followed by WQ, the structure Fatigue resistance is determined after heat
of the distance to the quenched area. of the sample obtained is entirely martensitic. treatment and quenching. Table 3 summarizes

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 Heat Treating of Boron Steels / 183

the results of different heat treatments of
22MnB5 AM FCE steel, 2.65 mm (0.1 in.)
thick, after fatigue testing by cyclical tensile
loading with a load ratio of Rs = 0.1. Speci-
mens were austenitized at 950  C (1740  F)
for 5 min. The fatigue resistance of ArcelorMit-
tal’s boron-quenchable steels is 40 to 60%
higher than that of S355MC AM FCE low-alloy
grade. It can be reduced by over 30% if total
decarburization is carried out.
Low-Alloyed Boron Steel. Boron, in the
presence of C-Mn-Mo-Cr, increases the harden-
ability to many times that of unalloyed steel
(Ref 18). Many grades in these categories are heat
treatable boron-containing steels (Table 4) with
improved hardness and wear properties. The criti-
cal cooling rate for these steels is considerably
lower than that for C-Mn-B steel. The Society of
Automotive Engineers (SAE) has designated
these grades with an H suffix to denote harden-
ability where it is a major requirement. Carbon
steels and alloy steels are designated by a four-
digit number, where the first digit indicates the
main alloying element(s), the second digit indi-
cates the secondary alloying element(s), and the
last two digits indicate the amount of carbon, in
hundredths of a percent by weight (Ref 19).
Figure 10 shows hardenability curves of the
boron low-alloyed steels (13MnCrB5) compared
to the steel without boron (16MnCr5). An addi-
tion of 30 ppm of boron in steel that contains
approximately 0.15% C, 1% Mn, and 0.9% Cr
shows a clear increase in hardness of almost
50% to a larger depth from the surface as com-
pared to a steel of identical composition but free
from boron (Ref 5). According the same authors,
there is no difference in hardness on the surface
between the boron-containing and the boron-free
steel, which can be seen in the Fig. 10. Accord-
ingly, the incipient hardness is determined, not
by boron, but by the martensitic structural state
influenced by the carbon content. The hardness-
enhancing effect of boron comes into play only
below the surface.
Boron-alloyed 22MnB5 steel has acceptable
hardenability and produces fully lath martensitic
microstructure after hot stamping. Yield strength
and UTS after hot stamping are increased to
approximately 1000 MPa (145 ksi) and 1500 MPa
(217.5 ksi), respectively, in a detailed study on
heat treatable C-Mn-Cr-B steel (Ref 20). Figure 11
shows YS and UTS of low-alloyed manganese-
boron steel (0.2% C, 1.25% Mn, 0.28% Si,
0.023% Ti, 0.15% Cr, and 25 ppm B) (Ref 21).
The thermal treatment was carried out by heating
the sample in the austenite single-phase range
(900  C, or 1650  F), holding it for 300 s, and
quenching it in different media such as air, oil,
and water. Although the trend of increasing
strength with increasing cooling rate is similar to
that of low-carbon unalloyed steel, a remarkable
change can be observed when the absolute values
at different cooling rate are observed. The
increase in YS in the OQ condition as compared
to the AC condition is greater than the increase
in the WQ condition as compared to the OQ con-
dition, and a similar trend is observed in UTS.
Yield strength in the WQ state is found to be
2.25 times higher than that in AC, whereas UTS
is 2.57 times higher. Figure 12 shows micrographs
of samples subjected in the AC and OQ states,
respectively, and the martensitic structure can be
clearly seen even in the OQ state, whereas it could
be observed in low-carbon unalloyed steel in the
WQ state (Ref 20).
These findings clearly indicate that boron
alone is not significantly contributing to the
increase in hardenability; rather, it is essential
to have other alloying elements. The synergistic
effect of boron with chromium and manganese
has led to an increase of 2.5 times in the strength
of as-rolled steel when subjected to austenitizing
followed by water quenching, and an increase of
1.5 times for unalloyed steel.
Carburized State. Case-carburized (CC) low-
carbon steels containing nickel, chromium, and
molybdenum alloying elements are widely used

Table 2 Typical mechanical properties of a 6 mm (0.2 in.) specimen in the rolling direction Table 3 Fatigue resistance of 22MnB5 AM
before and after quenching FCE steel
As-received Quenched Endurance Spread Maximum
Specimen heated for
limit (sD) (s) stress (sD)
Re Rm Re Rm 5 min at 950  C (1740  F)
followed by: MPa ksi MPa ksi MPa ksi
Grade MPa ksi MPa ksi A, % Hardness, HRC MPa ksi MPa ksi A, %
Water quenching 253 36.7 6 0.9 562 81.5
22MnB5 AM FCE 350 50.8 520 75.4 27 45 1100 159.5 1500 217.6 10 Oil quenching 260 37.7 5 0.7 578 83.8
30MnB5 AM FCE and EN 10083 440 63.8 660 95.7 25 50 1200 174.0 1700 246.6 8 Water quenching + heat 293 42.5 26 3.8 651 94.4
30MnB5 DRUM AM FCE 530 76.8 750 108.8 21 N/A treatment at 200 C
38MnB5 AM FCE 480 69.6 760 110.2 18 55 1300 188.5 2000 290.1 7 (390  F) for 20 min
Re: yield strength; Rm: ultimate tensile strength
sD = (smax – smin)/2

Table 4 Heat treatable boron-added SAE grades of steel

Composition, %
SAE grade C Mn Si(a) P(a) S(a) Cr Ni(a) Mo(a) B

Standard alloy steel 50B46 0.44–0.49 0.75/1.00 0.15–0.35 0.035 max 0.040 max 0.20–0.35 0.25 max 0.06 max 0.0005–0.003
51B60 0.56–0.64 0.75/1.00 0.15–0.35 0.035 max 0.040 max 0.70–0.90 0.25 max 0.06 max 0.0005–0.003
Standard H steels 50B40H(b) 0.37–0.44 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.30–0.70 0.25 max 0.20 max 0.0005–0.003
50B44H(b) 0.42–0.49 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.30–0.70 0.25 max 0.20 max 0.0005–0.003
50B46H(b) 0.43–0.50 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.13–0.43 0.25 max 0.20 max 0.0005–0.003
50B50H(b) 0.47–0.54 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.30–0.70 0.25 max 0.20 max 0.0005–0.003
50B60H(b) 0.55–0.65 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.30–0.70 0.25 max 0.20 max 0.0005–0.003
51B60H(b) 0.55–0.65 0.65–1.10 0.15–0.35 0.030 max 0.040 max 0.60–1.00 0.25 max 0.20 max 0.0005–0.003
81B45H(b) 0.42–0.49 0.70–1.05 0.15–0.35 0.030 max 0.040 max 0.30–0.60 0.15–0.45 0.08–0.15 0.0005–0.003
86B45H(b) 0.42–0.49 0.70–1.05 0.15–0.35 0.030 max 0.040 max 0.35–0.65 0.35–0.75 0.15–0.25 0.0005–0.003
94B15H(b) 0.12–0.18 0.70–1.05 0.15–0.35 0.030 max 0.040 max 0.25–0.55 0.25–0.65 0.08–0.15 0.0005–0.003
94B17H(b) 0.14–0.20 0.70–1.05 0.15–0.35 0.030 max 0.040 max 0.25–0.55 0.25–0.65 0.08–0.15 0.0005–0.003
94B30H(b) 0.27–0.33 0.70–1.05 0.15–0.35 0.030 max 0.040 max 0.25–0.55 0.25–0.65 0.08–0.15 0.0005–0.003
Standard carbon and carbon boron H Steels 15B21(a) 0.17–0.24 0.70–1.20 0.15–0.35 0.03 max 0.05 max ... ... ... 0.0005–0.003
15B28H 0.25–0.34 1.0–1.5 0.15–0.35 0.03 max 0.05 max ... ... ... ...
15B30H 0.27–0.35 0.70–1.20 0.15–0.35 0.03 max 0.05 max ... ... ... ...
15B35H(a) 0.31–0.39 0.7–1.20 0.15–0.35 0.03 max 0.05 max ... ... ... 0.0005–0.003
15B37H(a) 0.30–0.39 1.0–1.5 0.15–0.35 0.03 max 0.05 max ... ... ... 0.0005–0.003
15B41H(a) 0.35–0.45 1.25–1.75 0.15–0.35 0.03 max 0.05 max ... ... ... 0.0005–0.003
1B48H(a) 0.43–0.53 1.0–1.5 0.15–0.35 0.03 max 0.05 max ... ... ... 0.0005–0.003
15B62H(a) 0.54–0.67 1.0–1.5 0.40–0.60 0.03 max 0.05 max ... ... ... 0.0005–0.003
(a) Unless specified. (b) Boron in steel = 0.0005 to 0.003. Note: For electric furnace steels, phosphorus and sulfur = 0.025 max and the prefix E is added.

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 184 / Heat Treating of Carbon and Low-Alloy Steels
Fig. 10 Boron-effected hardenability of steel. Source:
Ref 5
for transmission gears in automobiles, because
they possess desirable mechanical properties. In
order to cut costs and conserve scarce materials
such as nickel and molybdenum for strategic
applications, a boron-alloyed steel has been devel-
oped with properties found to be comparable to
those of Ni-Cr-Mo alloyed steel and superior
to those of conventional boron steel (CBS)
(Ref 22). In the process of its development, care
was taken to ensure the precipitation of boron,
which results in precipitation hardening.
The chemistry of the three steels is shown in
Table 5. Table 6 shows the high cleanliness
level of the developed boron steel (DBS) in
terms of inclusion rating test results conducted
as per ASTM E 45. The study concludes:
 Developed boron steel was comparable to
the existing Ni-Cr-Mo alloyed gear steel
(EN353 of BS 970 standard) and superior
to CBS (20MnCr5B). Developed boron steel
specimens failed at an average impact load of
53.1 kN, comparable to 54 kN of Ni-Cr-Mo
alloyed steel and higher than 38.68 kN of
CBS.
 Tensile strength of DBS was highest (789 MPa,
or 114.4 ksi) whereas elongation of CBS was
highest (11.73%). Tensile strength (679 MPa, or
98.5 ksi) and elongation (9.18%) of Ni-Cr-Mo
alloyed steels was in between the two boron
steels.
 For DBS and Ni-Cr-Mo alloyed steel gears,
distortion of inside diameter (ID) and width
due to carburization was comparable to aver-
age of 0.225 mm (0.009 in.) and 0.05 mm
(0.002 in.), respectively. However, distortion
of ID and width of CBS gears was higher:
0.400 mm (0.016 in.) and 0.09 mm (0.004 in.),
respectively.
 Lower distortions of Ni-Cr-Mo alloyed steel
were associated with higher retained austenite
compared to CBS. However, lower distortion
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1200 174 1800 261
1060 1600 1637 232
Tensile strength, MPa
1000 145
Yield strength, MPa
Tensile strength, ksi
1400 203
Yield strength, ksi
1005
800 116 1415
1200 174
600 87 1000 145
471 800 116
400 58 600 637 87
200 29 400 58
200 29
0 0
0 0
AC OQ WQ
AC OQ WQ
Cooling condition
(a) (b) Cooling condition
Fig. 11 Effect of boron on (a) yield strength (YS) and (b) ultimate tensile strength (UTS) with varying cooling rates
when cooled from austenitizing temperature of 900  C (1650  F). AC, air cooling; OQ, oil quenching;
WQ, water quenching
of DBS gears could be due to controlled and
uniform grain size distribution.
 Lower distortion in the DBS against CBS
saves finished component cost in terms of
tool repair or replacement period, thereby
increasing the productivity.
 With this huge potential of enhanced mechani-
cal properties, lower raw material cost, reduced
machining requirements, and higher cost sav-
ings, DBS can be considered as alternative steel
for transmission gears against costly Ni-Cr-Mo
alloyed steels and inferior CBS.
Heat Treatment Simulation
The addition of boron increases the harden-
ability of quenched and tempered steels. How-
ever, the extent of hardening depends on the
transformation characteristics of austenite to
ferrite and the presence of other alloying ele-
ments. With the recent availability of advanced
thermomechanical simulators, heat treatment
studies can be carried out more precisely
(Ref 23–25). The austenite-to-ferrite transfor-
mation is accompanied by an increase in the
atomic volume of the transformed phase; the
resulting dilation in the test specimen is linked
with the kinetics of transformation. The change
in diameter of these specimens during cooling
was recorded using an ultrasensitive dilatome-
ter provided with the simulator, and the output Fig. 12 Microstructures of (a) air-cooled and (b) oil-
of the dilatometer, that is, the “dilatation plot,” quenched heat treated sample
was used in identifying the start and finish tem-
peratures of the transformed phase. Figure 13
shows a typical continuous cooling transforma- Ar3 temperatures of both the steels, when sub-
tion (CCT) diagram of unalloyed boron-added jected to varied cooling rates, showed similar
steel, constructed from data on the time taken trends with increasing cooling rate. This obser-
for start-to-finish transformations at different vation authenticates that austenitization at low
cooling rates. With the increase in cooling rate, temperature (950  C) causes boron to precipitate
the onset of ferrite transformation shifted to a as boron nitride, leading to an absence of dis-
lower temperature. solved boron in the lattice. As a result, boron
Figure 14 shows how the Ar3 temperature does not contribute to the hardenability of steel
varied with different cooling rates when the spe- and there is instead some softening, owing to
cimens were soaked at a low austenitizing tem- the removal of free nitrogen through a scaveng-
perature of 950  C (1740  F). These results ing effect. In contrast, a different kind of situa-
have been compared with the results of a dilata- tion emerged when boron-treated steel was
tion study (Ref 26) carried out with plain carbon austenitized at higher temperatures (up to
(0.04 wt%)-manganese (0.22 wt%) steel. The 1200  C, or 2190  F) followed by cooling at
 Heat Treating of Boron Steels / 185

Table 5 Chemistry of conventional boron steel, developed boron steel, and Ni-Cr-Mo steel Table 6 Inclusion rating of developed
Composition, wt%
boron steel (as per ASTM E 45)
Steel C Si Mn Cr Ni Mo B Al Ti Thickness A B C D
classification (sulphides) (aluminate) (silicates) (oxides)
Ni-Cr-Mo steel 0.17 0.35 0.80 0.98 1.6 0.17 Nil 0.020 Trace
Conventional steel 0.17 0.24 1.20 1.23 0.11 0.07 0.0019 0.020 0.020 Thin 2.5 1.5 0 1.5
Developed boron steel 0.18 0.22 1.24 1.21 0.14 0.04 0.0017 0.020 0.0019 Heavy 1.0 0.5 0 0.5

Cooling rate, °F/s

0 9 18 27 36 45
900 1656

Boron-added steel
880 1615
Boron-free steel

Ar3 temperature, °C

Ar3 temperature, °F
860 1580

840 1545

Fig. 13 Continuous cooling transformation diagram

of unalloyed boron-added steel
820 1510
varied rates (Fig. 15). The results show that the 0 5 10 15 20 25
increase in cooling rate leads to a significant Cooling rate, °C/s
decrease in Ar3 temperature at higher austenitiz-
ing temperatures (>950  C, or 1740  F). This Fig. 14 Comparison of Ar3 temperature variation with cooling rates for unalloyed boron-added and boron-free steels
(austenitizing temperature: 950  C, or 1740  F)
effect is particularly great at 1200  C (2190  F).
Figure 16 shows a typical continuous cooling
Cooling rate, °F/s
transformation (CCT) diagram for low-alloyed
0 18 36 54
boron-added steel (Ref 21). On each cooling rate 900 1650
curve, the proeutectoid ferrite start temperature
(Ar3), the pearlite start temperature (Ps), and the
pearlite finish temperature (Pf) have been 850 1560
marked. It can be inferred that all the curves
associated with different transformation tem-
Ar3 temperature, °C

Ar3 temperature, °F
peratures have diminishing tendencies as the 800 1470
cooling rates are increased. However, the
decrease is gradual up to a cooling rate of
5  C/s (9  F/s). The proclivity toward decline 750 1380
becomes quite sharp at and above cooling rates
of 10  C/s (18  F/s), and continues to be so until
it again levels off at cooling rates of 20  C/s 700 1290
(36  F/s) and beyond. The CCT diagram shows
the temperature at which proeutectoid ferrite is
first formed from austenite by the line labeled 650 1200
Ar3. There is not much variation in this tempera- 0 10 20 30
ture with cooling rates. The region between the Cooling rate, °C/s
Ar3 line and the the Ps line widens with increas-
Austenitizing temperatures
ing cooling rates. The lines representing Ps and 950 °C 1000 °C 1100 °C 1200 °C
Pf remain nearly parallel up to a cooling rate of (1740 °F) (1830 °F) (2010 °F) (2190 °F)
5  C/s. A marked change in the width of separa-
tion occurs after this cooling rate and the area
widens progressively as higher cooling rates Fig. 15 Variation in Ar3 temperature of unalloyed boron-added steel with cooling rate for different austenitizing
temperatures
are approached. Therefore, the cooling rate of
5  C/s is critical and seems to signal departure
from formation of a mere pearlite-ferrite phase pearlite phase mixture. However, in the latter, fraction has increased, as can be seen from
mixture. This may also be the cooling rate above the coarse pearlite colony size is slightly bigger. Fig. 17(d), obtained from a sample cooled at the
which bainite may form. The formation of proeutectoid ferrite has occurred rate of 20  C/s (36  F/s). These microscopic
Figure 17 shows scanning micrographs from along the prior-austenite grain boundary. From this examinations corroborate the inferences from
samples cooled at different rates. The microstruc- an estimate of average prior-austenite grain size the CCT diagram.
tures of Fig. 17(a) and (b) from samples cooled at can be made, which works out to be 130 mm. Recently, the original time-temperature-
slower rates of 0.5  C/s and 2  C/s (0.9 and The first indication of the formation of bainite transformation (TTT) diagram has been modi-
3.6  F/s) are completely dominated by ferrite- can be seen in Fig. 17(c). The bainite volume fied to reflect the boron effect in resistance seam

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 186 / Heat Treating of Carbon and Low-Alloy Steels

900 1650 Cooling rate in the incubation period until a concentration

Ar3 ºC/s (ºF/s)
800 1470 of approximately 20 ppm is reached, after
A+F
700
Ps
1290
0.2 (0.36) which the function becomes insensitive to boron
P+F Pf 0.5 (0.9) and the overall effect becomes unreliable. In
Temperature, ºC

600 Bs 1110
contrast, for medium-carbon (0.4 wt%) high-
1 (1.8)
500
Ms
930 manganese (1.5 wt%) steel, the addition of boron
400 A+B 2 (3.6) (40 ppm) was observed to enable some bainite
A+M 750
300
Bf
570 5 (9) and martensite formation at a cooling rate of only
Mf 10 (18) 0.6  C/s (1  F/s) (Ref 29). Even a slow cooling
200 390
rate, as low as <1  C/s (2  F/s), has suppressed
100 210 20 (36)
the formation of pearlite. In this case, the dra-
0 0 36 (64.8) matic effect on hardenability can be attributed
0.1 1 10 100 1000 10,000
to shifting the upper C-curve to the right by
Time, s
boron and shifting both the upper and lower
Fig. 16 Continuous cooling transformation diagram of low-alloyed boron-added steel C-curves to the right by carbon and manganese.

Applications

Boron steels are used for a variety of applica-

Fig. 17 Scanning electron micrograph from samples (a) 0.5  C/s (0.9  F/s), (b) 2  C/s (3.6  F), (c) 10  C/s (18  F/s),
and (d) 20  C/s (36  F/s)
welds of low-carbon unalloyed steel (Ref 27). In
this model, the initiation of transformation to
allotriomorphic ferrite from austenite is retarded
as a function of boron concentration in solid
solution in the austenite. Accordingly, TTT dia-
grams are plotted (Ref 20) for the onset and com-
pletion of reactions to form pearlite, bainite, and
martensite. These consist essentially of two
C-curves, one at a higher temperature represent-
ing reconstructive transformation to ferrite or
pearlite, and one at a lower temperature where
atomic mobility is diminished, representing a
displacive transformation to phases such as
Widmanstätten ferrite, bainite, and acicular fer-
rite (Fig. 18). Boron has the largest effect on
the C-curve for reconstructive transformation,
leaving the lower C-curve hardly changed. In
Fig. 18, the effect of cooling rate on the evolution
of microstructure has been shown schematically,
further corroborating the pronounced effect of
boron on the upper C-curve only.
The increase in the incubation period before
reconstructive transformation as a function of
soluble boron concentration has been investi-
gated quantitatively by Pickering (Ref 28). It
was found that there is a proportional increase
tions, as a wear-resistant material and as a high-
strength structural steel. Examples include
punching tools, spades, knives, saw blades, earth
scraper segments, track links, rollers, drive
sprockets, axle components, crankshafts, safety
beams, and so forth. Carbon-manganese-boron
steels are far less expensive than alloy steels of
equivalent hardenability. An expanding area of
boron usage is the field of HSLA and other struc-
tural steels. These may be supplied as hot rolled
or as quenched and tempered (for boron grades,
the latter are more common). Boron assures ade-
quate hardenability in heavier plate sections. The
type of boron steel used on vehicles today has an
extremely high yield point of approximately
1350 to 1400 MPa (196 to 203 ksi), approxi-
mately four times stronger than average high-
strength steel. Applications include dash panel,
safety bar around the rear seats, door guard
beams, B-pillars, bumper reinforcements, guard
beams, rear body panel, and so forth.
Boron is sometimes used in non-heat-treated
steels. Ferroboron may be added as an inten-
tional nitrogen scavenger in carbon steels for
automotive strip stock. By avoiding interstitial
nitrogen, boron makes the steel more formable.
Aluminum is sometimes used for a similar duty,
but AlN is slower to precipitate, requiring
higher annealing temperatures. Boron addition
makes the steel more formable and eliminates
the need for strain-age-suppressing anneals.
Boron has a high neutron absorption capabil-
ity. For this reason, it is added to certain types
of stainless steel for use in the nuclear industry.
Levels of 4% B or more have been used, but the
lack of hot ductility and weldability means that
boron contents of 0.5 to 1.0% are more com-
mon for neutron absorption application. None-
theless, even at these boron contents, the
ferroboron must be of the highest purity.
Advantages of boron steels are improved cold
formability; lower delivered hardness, giving
improved blanking tool life; improved weldabil-
ity due to low carbon equivalents; lower temper-
ing temperatures, providing energy savings; and
good case-hardening response.

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 Heat Treating of Boron Steels / 187

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Reconstructive transformation
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