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Abstract
rntroduction
The mechanical properties of advanced high strength steels
(AHSS) are sensitive to their multi-phase microstructures.
Phosphorous is added in AHS
strengthener and to suppress
thereby enhancing the room
austenite in transformation in
quench and partitioning (Q&P) steels' However, the
weldability of phosphorous containing steels is poorer than
conventional low carbon steels due to embrittlement resulting cycles of welding processes destroy the original
from the segregation ofphosphorus to grain boundaries during microstructure. In addition, alloying elements present in the
solidification of the weld pool. In order to reduce the grain
boundary embrittlement, the addition of boron has been
suggested; however, this also increases hardenability and the
rato of boron to other alloying elements present in the steels
also affect the mechanical properties of the welds.
In this work, the partitioning behaviour of phosphorous and
boron during the solidification of weld pools under various
weld thermal cycles has been studied using experimental
simulations and a DictrarM based diffusional model. Steels
and boron contents were
welding thermal cYcles' galvanisability t3l-t61. Phosphorous is also known to suppress
ated bY hardness, cross ihe formation of cementite and thereby increase the amount of
tension tests and correlated with the weld microstructure' austenite retained at room temperature [3]' However' the
Diffusion calculations show that the phosphorus concentration segregatio
in the last area in the weld pool to solidiff can reach about welding I
0.38 wt. o/o for a steel with a bulk concentration of 0.08 wt' %' complex
Elemental analysis indicates that in the absence of boron, the elements
grain boundaries of columnar grains in the weld pool are
decorated with phosphorous. As a result, a complete interface
failure occurs during cross tension testing. With the addition
of boron, apart from an increase in weld strength, the failure
mode switches to a complete plug mode'
Keywords
Elements, wt. 7o c P B
Steel-CP 0.07 0.08
Vickers hardness measurements with a load of 200 g were
r4 0.08
made to examine the hardness variations across the width of
Steel-2CP 0.
J
possibilities of 1
weldabilitY and
Figure 2: 'L' shaped specimenfor tensile shear tesls' The spot
the segregation
weld size is of about 6 mm diameler'
-2CP contained
0.07 and 0.14 wt. Yo carbon respectively. Samples were cut The carbon and phosphorous partitioning behaviour during
into 50 x 100 mm2 coupons and held for 2 days under vacuum solidihcation of Steel-CP and Steel-2CP (table l) was
(10-a mbar) at 1473 K in order to homogenise and solution
simulated using finite difference based diffusion and kinetics
nneal. 5 x l0 mm2 samples were subsequently cut and calculation toft*u.. DictrarM coupled with thermodynamic
zone (HAZ) weld thermal cYcles
software ThermocalcrM' Database TCFE3 was used for phase
rmo-mechanical simulator. During
equilibrium and, thermodynamic and mobility data were
were continuouslY heated to Peak
obtained from the MOB2 database.
temperatures ranging from 673 ro 1473 K at a heating rate of A rectangular 100 x 100 rm2 system with 5O-grid points was
200 K s-1. After reaching the desired peak temperatures, cooled fiom 1850 K at 10,50 and 100 K s-'' An adaptive
samples were then cooled to room temperature at an average
coolng rate of ll5 K s-r. Figure I shows the thermal cycles
used t simulate the heat affected zone on the steel samples
used in this study.
free steels, as the MOB2 database did not contain mobility solidihed -fenite subsequently transforms into austenite and
data ofboron in steel. the system becomes completely austenitic when the
Samples for microscopy analyses were prepared after etching temperature reaches 1693 K under equilibrium conditions' In
the polished samples with 4 o/o Nital solution for 5 s' Optical St;l-2CP, austenite starts to form from the liquid and the -
microscopy analysis was carried out using an Olympus fenite by a peritectic reaction starting from 1765 K. Steel-2CP
BX60Mrr optical microscope equipped with image capturing becomes completely austenitic at 1738 K under equilibrium
and analysis software analySlSrM. Scanning electron condition.
microscopy (SEM) was performed using a JEOL JSM
6500FrM - field emission gun (FEG). Electron probe
microanalysis (EPMA) was carried out to analyse elemental Heat affected zone simulations
distributions in the fusion zones of resistance spot welded The microscopy analysis clearly shows that peak temperatures
samples. The measurements were performed in a JEOL JXA influence the microstructural constituents. Figures 4, 5 and 6
8900R microprobe using an electron beam with energy of l0 show the microstructures of the steel samples (table-l), treated
keV and beam current of 200 nA employing Wavelength with HAZ thermal cycles.
Dispersive Spectrometry (WDS). The composition at each
analysis location was determined using the X-ray intensities of
the constituent elements after background correction relative
to the corresponding intensities of reference materials. The
intensity ratios were processed with a matrix correction
program CITZAF [20]. The backgrounds of the light elements
B and C were measured on the spectral line wavelength
position using a pure Fe standard. Each analysis location was
decontaminated using an air jet during the measurement' The
points of analysis were located along a line with increments of
5 rm and involved the elements B, C and P. The energy of the
spectral lines, detection limit and counting efiors are given in
table 3.
Counting
Energy, Detection
Element, X-ray line error, Figure 4: Microstructures of Steel-CP samples lreated with
keV limit, ppm o/o
wt. HZ thermal cycles with peak temperature indicated' (F-
Boron, B Ka 0.1 85 50 0.02
ferrite, B-bainite and M-martensite).
Carbon, C Ka 0.282 100 0.02
Phosphorous, P Ko 2.013 30 0.01
Results
The quasi-binary phase diagram of the steels used in this work
is shown in figure 3.
1850
Liqud
1800
Y
E )-
s
8.
E
o
t-
1600
00 0.2 0.4 06 08 10
Caron, wt. %
solidifcation
(c)- too Ks'l
The carbon and phosphorous partitioning behaviour during the
solidification of steels was simulated using DictrarM' In this 0.8
from 1850 K. In contrast to Steel-CP, solidification of liquid ot (a)-t'o xt, (-so xt-' and(c)-100 Ks-t'
of Steel-2CP completes after relatively longer times namely
ll.2 and2.5 s at 10 and 50 K s-r respectively' 'When cooling at The partiti observed for
100 K s-r, 0.35 volume fraction of liquid is still present in duringthe of Steel-CP
Steel-2CP even after I s, whereas, Steel-CP completely in figure K s-1, the
solidif,res at this cooling rate. concentrat high as 0.71
the cooling rates from 1850 K increase, the phosphorous
concentration of the liquid in the final stages of solidification solidification. While the phosphorous content of unsolidihed
decreases in contrast to carbon. This is due to the faster liquid decreases with increasing cooling rate in Steel-CP, in
diffusion of carbon from the solidihed -fenite to the liquid Steel-2CP, at 50 K s-r, phosphorous content ofthe liquid at the
compared to phosphorous. After 1.9 s, the phosphorous end of the solidihcation is much higher (l.l wt. %) than while
concentration in the liquid is 0.65 wt. % during cooling at a cooling at l0 K.-' 10.5 wt.%). This behaviour indicates the
rate of 50 K s-l and it reaches to 0.38 wt. % for the cooling influence of the peritectic reaction on the segregation of
rate of 100 K s-r just before the completion of solidification phosphorous in unsolidified liquid, which. may be present in
(0.e . the inter-denritic boundaries. At 100 K s'', while the system
During the solidification of Steel-2CP, the carbon partitioning contains about 35 % liquid, the phosphorous in liquid is as
to the liquid is strongly influenced by the onset of the high as 0.55 wt. % which may increase during the course of
peritectic reaction. The liquid initially solidihes with a strong solidihcation.
pafitioning of carbon and phosphorous from solidified -
ferrite (figure 9). Austenite nucleates from the liquid/-fenite Influence of elemental segregation on the mechanical
interface at around 1760 K while cooling fom 1850 K at 10, ProPerties of the welds
50 and 100 K s-r, which is after 9, 1.8 and 0.9 s respectively' The microstructure of the resistance spot welded samples
Due to this, a local partitioning of carbon and phosphorous is primarily contains martensite in the fusion zones, after
observed after this time period (indicated by arrows in figure welding using the parameters given in table 2' Figure 10
9). A sharp peak of phosphorous is observed at the - shows an overview of the fusion zones of the welds'
fenite/austenite interface in contrast to carbon due to the slow Mechanical properties of resistance spot welded Steel-CP and
diffusion of phosphorous. At 100 K s-r, the -ferrite/austenite Steel-2CP were evaluated using a tensile shear test (LTS) and
interface contains as much as 0.2 wt. % phosphorous and the Vickers hardness measurements. The results were compared
solid/liquid interfaces contain about 0.56 wt. Yo aftet cooling with Steel-CPB to study the influence of boron on the
from 1850 K for I s at a cooling rate of 100 K s-r (hgure 9). mechanical properties of the welds.
C-l0Ks-r P-l0Ks-r
C-l0Ks l0
P_IOK 0
*
E
E
q 8
f t
I
.
'\--
o 0
g tE
I
0 I E I
0
v
01
0
Dbln, m oshE. m
't0-6
Dilan. m Dlsln@, m
0
C-50Ks-r P-50Ks-t 9
l5
C-50K 2.4
P-50K
l 0,5
C
E
t
t j
t65
i
0 e
0 -
O
0.
0t '->+.---\ F I
I
I
01 v
ol8tmo. oislrc, m
-#-ill.
45
Ol3lsn@. m Dislan, n
09
C-l00Ks-r ot
P-l00Ks-r
e
I -l00Ks
t i
E l
I
O
0l e
b
0
0l I I
02 2.
1o
C-l00Ks-'
Dlslane m D6nG m
o.t0
ll78 and ll83 K, respectively. This may due to a partial
o.oo '
000 austenisation resulting from a fast heating rate' Moreover,
Posltion (um) microstructural observation indicates that the martensite
volume fraction in Steel-CPB after heating to a peak
Figure I 5; Elemental distribution at the centre of the fusion
zone of Steel-CP weld (see lable 3 for measurement errors)'
l.
o.s
0.
S
o,ro
-c.@r
formation of fenite during cooling from austenisation
.lc 0.. temperatures [l4]. Thus, it is possible that in the case of Steel-
,9 0.50 CPB which contained about 2'l ppm of carbon, a higher
I o.ro amount of martensite is found after cooling from 1273 K' In
contrast to Steel-CP and Steel-CPB, Steel-2CP showed an
I o.:o
(J
0.20 almost complete martensitic microstructure after heating to
1273 K. This is due to the presence of a higher amount of
carbon (0.14 wt. %), which resulted in reduced A"
0,10
0.w
5m
Posltio (rn)
temperature.
The solidihcation kinetics calculated from the DictrarM based
Figure l6: Elemental distribution at the centre of thefusion solidihcation model for Steel-CP and Steel-2CP, indicate that
zone of Steel-2CP weld (see table3 for measurement errors)
1,00
0.90
^0.10
S o.ro
l -C{o
0..0
c -korr
po 0.50
S o,ro
E o.:o
o
I o.ro
Positlon (Fm)
before the completion of solidification' However, local
partitioning ofcarbon at the liquid/-ferrite interface may lead
Figure 17: Elemental distribution at the centre of thefusion io non-.quilibrium nucleation of austenite for steels, which
zone of Steel-CPB weld (see table 3 for measuremenl errors)' solidifu to -fenite as a primary solidif,ing component
1231,1241.
I)iscussions ine iftrsion calculations carried out during the solidification
of the steels clearly showed the effect of cooling rates, bulk
The partitioning behaviour of carbon and phosphorous during concentration and the onset of the peritectic reaction on the
resisiance spot welding has been studied in steels containing elemental partitioning between the liquid and the solidification
front. In both Steel-CP and Steel-2CP, just before the
li
completion of solidihcation, the to
and
0.5 wt. % of carbon (figures 8 lk
carbon contents of 0.07 and 0'14 of
reaction starting from 1765 K' In steels, segregation of carbon is crucial in determining the mechanical properties of
alloying elements begins from the onset of solidihcation due the weld, as it may lead to the formation of brittle carbides at
to the difference in solubility of alloying elements between the inter-dendritic boundaries. The EPMA measurement
liquid, -fenite and austenite. Thus, it is important to compare carried out in the centre of the fusion zones of resistant spot
the solidihcation behaviour of Steel-CP and Steel-2CP to
welded samples also conltrms partitioning behaviour of weld zones of Steel-2CP showed a higher hardness than Steel-
carbon (figures 15 and 16). At some locations, the carbon CP and Steel-CPB, due to the presence of more carbon (hgure
concentration is more than I wt. % and found to vary from 0,3 l1).Wi fSteel-CPB showed a
to 0.5 wt. o when it is measured at the grain boundaries. slightly due to the Presence of
Despite having double the amount of carbon in the bulk of boron. in these steels showed
Steel-2CP, similar amounts of carbon were found in the that in presence of boron, an increased amount of martensite
unsolidifed liquid for a given cooling rate from 1850 K was found in Steel-CPB in comparison with Steel-CP. This
(figure 8 and 9). The onset of the peritectic reaction triggered leads to an increase in the hardness ofthe weld zone of Steel-
local partitioning of carbon to the newly formed austenite CPB.
from the -fenite. As the solubility of carbon in austenite is The addition of boron to steel also significantly increased the
higher than in -fenite, carbon also partitions to austenite and tensile shear strength ofthe welds (table 4). Strength increased
thereby reduces the amount of carbon that diffuses to the from 1.6 to 3.9 kN. It is also important to note that the weld
unsolidified liquid. diameter of the boron added Steel-CPB is higher (8.1 mm)
Similar partitioning behaviour was also found for phosphorous than Steel-CP (6.8 mm)' This is due to the increase in
during solidification. The phosphorous concentration in the maximum welding current Imax used for the resistance spot
unsolidified liquid was found to vary from 0'3 to 0'7 wt' % welding. In an earlier study, it was reported that the addition
(figures 8 and 9) and this result was also confirmed by the of boro resulted in larger welds, compared to steels without
EPMA measurements (figures 15 and.16)' In one case when boron due an increase in the contact resistance of boron
Steel-2CP was cooled at 50 K s-r from 1850 K, the containing steels [14]. In the present study, with an addition of
phosphorous content at the liquid was found to be as high as 27 ppm of boron, Imax, the highest welding current before
about I wt. %. EPMA measurements carried out in the fusion whiih splashing occurs increased to 7'85 kA for Steel-CPB
zone of a Steel-2CP weld showed that at some locations, from 7.25 kA (Steel-CP)'
phosphorous concentrations indeed reached to 0.8 wt. % Apart from an increase in strength, the failure mode of boron
(figure l6). Thus, even with a bulk phosphorous concentration added Steel-CPB was found to be a complete plug failure as
of 0.08 wt. Yo, it is possible to have localised regions in the compared to partial or full interface failure of Steel-CP and
fusion zone with a very high phosphorous concentration Steei-ZCp (figures 12-14). During the tensile shear testing, the
rations of weld of Steel-CPB did not fail and a failure was observed in
complex the HAZ. By contrast, in welds of Steel-CP and Steel-CPB,
elemental cracks were found to initiate at the fayed interfaces and
boundary propagated along the grain boundaries at the centre of the
embrittlement. fution ,on". The results of the tensile shear tests show that
When the cooling rates from 1850 K increase, the with an addition of 27 ppm of boron, the mechanical
alloying elements. induced plasticity steels", Met. Mat' Trans' A, Vol' 3lA,
. When the cooling rates increase during solidification, the
carbon concentration of the liquid increases, whereas
phosphorous content decreases due to the slow diffusion
ofphosphorous from -ferrite to liquid'
. Addition ofboron increases the hardness ofthe welds due
to the increase of martensite volume fraction in the heat
affected zones for the steels with a similar carbon
concentration.
. The mechanical properties of steel welds is improved with
the addition of boron. Boron was found to suppress the
grain boundary segregation of phosphorous thereby
reducing the embrittlement of the welds.