Journal of Materials Processing Tech.

255 (2018) 760–764

Contents lists available at ScienceDirect

Journal of Materials Processing Tech.

journal homepage: www.elsevier.com/locate/jmatprotec

Resistance upset welding of Zr-based bulk metallic glasses T

a,⁎ b a
Angelo Fernandes Andreoli , Jéssica Bruna Ponsoni , Carolina Soares ,
Marcelo Falcão de Oliveiraa, Claudio Shyinti Kiminamib
a
Materials Science and Engineering Department, São Carlos School of Engineering, University of São Paulo, Avenida João Dagnone, 1100, CEP 13563-120, São Carlos,
SP, Brazil
b
Materials Science and Engineering Department, Federal University of São Carlos, Rodovia Washington Luís, Km 235 C.P.147 – Jardim Guanabara, CEP: 13565-905, São
Carlos, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Zr-based bulk metallic glasses represent an emerging important class of structural materials with interesting
Bulk metallic glass (BMG) properties due to its amorphous nature. In this study, the structural and microstructural transformations to the
Amorphous metals heat-affected zone of a Zr-based bulk metallic glass welded by the resistance upset technology were investigated.
Crystallization X-ray diffraction, optical and scanning electron microscopy were used to characterize the base metal and the
Welding
heat-affected zone. Vickers microhardness testing was performed to assess the mechanical response of the
Resistance upset welding
welded joints. The amorphous phase volume fraction measured along the welded joints shows no difference
between the base metal and the heat-affected zone. It was possible to achieve a sound weld with no crystal-
lization of the base metal.

1. Introduction a Zr-based BMG by the resistance welding method. Kuroda et al. (2009)
used a thermomechanical simulator to weld Zr-based metallic glasses
Since the first metallic Au75Si25 glassy alloy was synthesized from with 50 μm thickness samples. An important conclusion from their work
the melt (Klement et al., 1960), much scientific effort has been devoted is that the welding time plays a major role controlling crystallization
to elucidate the physical-chemical and mechanical properties of during welding. When the temperature rises above the Tg, the time for
amorphous alloys. In the late 1980′s, the greater stabilization of the crystallization to occur is shortened. Consequently, longer welding time
supercooled liquid started the production of the so-called bulk metallic increases the crystallization rate. Makhanlall et al. (2012), conducted
glasses (BMGs), which increased the maximum sample thickness (tmax) experiments with resistance spot welding of a glassy
for many glassy metal systems, including Zr-based alloys (Inoue and Ti40Zr25Ni3Cu12Be20 and observed that the welding current and
Takeuchi, 2011). The development of bulk metallic glasses overcame welding time exerted a strong control over the amorphous nature of the
two of the three major challenges to establish metallic glasses as en- weld nuggets produced. With the increase in welding energy, weld
gineering materials: limitation of size (diameter or length) and lack of nugget and crystalline volumetric fraction tend to increase. While the
workability, related to low ductility (Yokoyama et al., 2008). Welding nugget diameter increase produces mechanically stronger joints, the
of BMGs is still a topic for research. increase in the crystalline volumetric fraction weakens the welded joint.
Full or partial crystallization at the joining zone of BMGs, during They also conclude that with the correct setup of welding parameters
welding, is well known to cause failure due to crack formation in the (time and current), the crystalline volumetric fraction of the molten
crystalline compounds formed (Kuo et al., 2010). Therefore, it is sub- zone and the heat affected zone (HAZ) can be reduced to a minimum.
stantial to evaluate welding processes and parameters that favor the The resistance upset welding process (UW) combines the Joule af-
glassy phase and avoids crystallization. In the supercooled liquid zone fect and pressure to bond metals pieces (Kerstens and Richardson,
(ΔTx), defined as the difference between the crystallization temperature 2009). It involves the interaction of electrical, thermal, mechanical and
(Tx) and the glass transition temperature (Tg), metallic glasses behave metallurgical phenomena (Zhang and Senkara et al., 2017). Two types
as a Newtonian fluid and can, therefore, be forged with ease. The su- of resistances characterize this welding process, namely, contact re-
percooled liquid interval is the optimum temperature range for welding sistance and bulk resistance. At the start of the welding process, contact
since no crystallization is expected. resistance plays a major role but, gradually it decreases, and the role of
Oliveira et al. (2001) were the first to disclose a successful joining of bulk resistance becomes more important. The advantages for welding

⁎
Corresponding author.
E-mail address: [email protected] (A.F. Andreoli).

https://doi.org/10.1016/j.jmatprotec.2018.01.034
Received 14 October 2017; Received in revised form 21 January 2018; Accepted 22 January 2018
Available online 20 February 2018
0924-0136/ © 2018 Elsevier B.V. All rights reserved.
A.F. Andreoli et al. Journal of Materials Processing Tech. 255 (2018) 760–764

metallic glasses are: (1) it is a solid-state process (2) no filler metal is The bonding surfaces were mechanically grinded up to 600-mesh
required, (3) short welding time, (4) ease of operation (Sharifitabar using SiC abrasive paper to improve contact resistance. Then it was
et al., 2011), and finally (5) low cost. cleaned by an ultrasonic treatment in acetone for 300 s. All welds were
One of the limitations of BMGs is their processing route. To suppress done under an argon flux of 10 l/min to avoid surface oxidation. A FLIR
the nucleation and growth of crystalline phases during solidification, T650sc thermal imaging camera was used, according to Shin et al.
there is a need for considerably high cooling rates compared to con- (2005), to record peak temperature (Tp), heating and cooling rates and,
ventional casting. This limits the maximum size in which a BMG can be heat distribution in the samples interface. The heating rate was de-
formed. Consequently, welding of these materials becomes of great termined from room temperature up to Tp. Cooling rate was determined
concern not only for scientific advancements but for practical purposes from Tp to Tg. Vickers microhardness was measured using a BUEHLER
as well. Welding BMGs allows to manufacture parts of greater size. The VH1102 model at the joining interfaces and positions −1 and +1 mm
aims of this study were to investigate the influence of the UW process in from the interface with a 2 N force.
the microstructure and hardness of the HAZ of a The resistance upset welding process was selected to weld Zr-based
Zr52.5Ti5Cu17.9Al10Ni14.6 BMG. BMGs for being a solid-state welding technology. In comparison with
fusion welding processes, the metallurgical properties and chemical
composition are not significantly modified leading to better mechanical
2. Experimental procedure properties (Kanne, 1993). Temperatures are lower than for fusion
welding, and there are no solidification stresses induced by melting.
Samples were prepared by arc melting in a purified inert gas at- The fact that is a solid-state process enabled to weld within the ΔTx, and
mosphere from a commercial ingot of the Vitreloy 105™ (VIT 105) hence below the BMG Tx. This feature allied to short welding cycles and
alloy. The nominal composition of the alloy is Zr52.5Ti5Cu17.9Al10Ni14.6 high cooling rates permitted the hypothesis that, with correct welding
(at.%). The suction-cast process in a copper mold, according to Deo and schedule, a HAZ without devitrification would occur.
Oliveira (2014), manufactured bulk glassy alloy rods. Rods of 4 mm in
diameter and 17 mm in length were cut with a slow-speed diamond saw
from the as-cast ingots for the welding procedure. 3. Results and discussion
Cross-sectional specimens were cut and mirror-like polished from
the as-cast ingot for microstructural characterization by optical mi- Fig. 1 presents the DSC thermogram of the as-cast VIT 105 BMG at a
croscopy (OM). Samples were etched with a solution of (10% HF; 90% 0.33 K/s heating rate. It is evident the Tg, Tx and the Tl at 394, 460 and
HNO3) 10/90 distilled water. The glassy nature of the samples was 825 °C, respectively. These results are in good agreement with the va-
confirmed by X-ray diffraction (XRD) using Cu Kα radiation. Tg, Tx and lues described by Hofmann et al. (2016). From the results, the width of
liquidus temperature (Tl) were determined by differential scanning the ΔTx was computed showing the good glass stability of this alloy
calorimetry (DSC) at a heating rate of 0.33 K/s according to ASTM composition. It is important to know the value of the ΔTx when welding
(2012). From these results, ΔTx was computed. Welded samples were BMGs since in this temperature interval it can be easily deformed
longitudinally cut, and polished specimens prepared for OM and scan- without devitrification occurring. The results from the DSC curve are
ning electron microscopy (SEM). The phases of the HAZ were identified summarized in Table 2.
by XRD using Cu Kα radiation with a 0.5° per minute step. The amor- Fig. 2 presents the diffraction pattern of the as-cast alloy. Only
phous phase volume fraction (Vf) at the welding interface (position 0) broad and diffuse peaks around 2θ (38° and 65°) are evident. These
and positions −10, −5, 5 and 10 mm from the interface were de- broad peaks correspond to the medium and short-range atomic ar-
termined using OM images and the ZEISS AxioVs40 V4.8.2.0 software rangements of the glassy phase respectively. The XRD technique has no
according to ASTM (2016), before and after welding. sensibility to detect crystal structures with volume fraction below
A partial factorial design with two factors (welding current and 3–5%, therefore, no crystalline peaks are revealed, despite minor
welding time), 3 levels for welding current, 2 levels for welding time, crystalline fraction was detected by OM. The Vf of the as-cast samples is
experiment was designed for the welding procedure. An extra weld with shown in Fig. 3. All samples have Vf above 98%. The mean Vf of the
higher welding energy was produced for comparison. For welding samples produced is 99.2 ± 0.36% for a 90% confidence interval.
current, the levels were 26, 28 and 30% of the nominal electrical cur- Fig. 4 shows the outer appearance of welded samples S3 and S6. One
rent of the welding machine. For welding time (t), 1.16 and, 1.25 s were
used. The welding pressure was setup at 1 MPa. A resistance upset
welder, 20 kVA AC, 60 Hz was used. The electrical data during the
welding process was collected using a MINIPA oscilloscope. An oscil-
loscope probe and a Rogowski coil were coupled to the electrodes and
the machine secondary conductor, respectively. From the electrical
data, the thermal energy was calculated according to equation 1.
Equation 1: Q = I 2Rt,where Q is the thermal energy during the process,
I is the welding current, R is the electrical resistance, and t stands for
welding time (Table 1). From this point on, samples are to be labeled
(S1, S2, S3, S4, S5, S6 and, S7), according to their thermal energies,
Table 1.

Table 1
Experimental design, sample labels and resulting thermal energies from the welding
operation.

Level

Welding current (%) 26 28 30 35

Welding time (s) 1.16 1.25 1.16 1.25 1.16 1.25 1.25
Sample label S1 S2 S3 S4 S5 S6 S7
Fig. 1. Differential scanning calorimetry (DSC) curve of the as-cast VIT 105 BMG at a
Thermal energy (J) 3157 3700 3770 4350 5750 5960 > 10000
0.33 K/s heating rate showing Tg, Tx and Tl.

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A.F. Andreoli et al. Journal of Materials Processing Tech. 255 (2018) 760–764

Table 2 different temperatures. For lower temperatures, the NiZr2 “big cube”
DSC results for the as-cast VIT 105 alloy. phase precipitates while annealing at higher temperatures the CuZr2
phase forms. For sample S7, the amorphous diffuse peak is barely no-
Tg (ºC) Tx (ºC) Tl (ºC) ΔTx (ºC)
ticed. It is a strong evidence that for the highest thermal energy, the
394 460 825 66 welding process occurred beyond the optimum ΔTx interval and, com-
plete crystallization of the HAZ occurred.
The thermal data acquired using a FLIR T650sc camera, during the
welding operation of samples S3, S4, S5 and S6 is provided in Table 3.
Tp, time interval above Tx, heating and cooling rates are described. For
samples S3 and S4, peak temperatures did not rise above the Tx mea-
sured by DSC at a 0.33 k/s (Table 2). Notwithstanding, sample S4 re-
vealed a very narrow crystallization line in the HAZ. It is known from
the literature that the heating rate affect both Tg and Tx. “The crystal-
lization process is largely retarded by a delay of the diffusion at a high
heating rate” (Ichitsubo et al., 2005). This is reasonable to explain why
S4 experienced crystallization in the HAZ while S3 retained its amor-
phous structure. Furthermore, the cooling rate for sample S4 was lower
compared to others. For samples S5 and S6 the time interval that
samples remained above the Tx was sufficient to provide the energy
needed for atom diffusion and the formation of crystalline compounds.
Ultimately, the formation of brittle crystalline phases in the HAZ cause
the joints to fail. The crystalline phases formed during the devitrifica-
tion of Zr52.5Cu17.9Ni14.6Al10Ti5 BMG are very brittle (Székely et al.,
2002). Cooling-induced thermal stresses potentially lead to the nu-
Fig. 2. XRD pattern of the as-cast VIT 105 base metal.
cleation and growth of cracks that propagate within the brittle crys-
talline network and terminate in the amorphous matrix (Kosiba and
Pauly, 2017).
The results from the Vf at different positions in the welded joints
(Fig. 6) corroborate the previous results. For samples with lower
welding energies (S1 and S3) no detectable changes in the Vf at the
interface (0 mm) and positions −10, −5, 5 and 10 mm are observed,
confirming that the welding process did not alter the amorphous
structure of the base metal. One may want to compare the Vf prior to
the welding process for all samples in Fig. 3. With increase in thermal
energy, the Vf decreases linearly in the welded zone approaching 0% at
the joining interface for the sample with the highest welding energy
(S7).
At this point, it is important to emphasize that for sample S1, despite
that no changes to the base metal microstructure occurred, only partial
bonding of the interface was achieved. This can be seen in the SEM
image of the interfacial zone of sample S1 (Fig. 7a). It is worth pointing
out that the interface acts as a preferential site for corrosion during
Fig. 3. The amorphous phase volume fraction of the as-cast VIT 105 samples S1, S2, S3, etching. Nevertheless, an obvious lack of joining in the interface can be
S4, S5, S6 and S7, before welding. observed. The microstructure of the interfacial zone of sample S5 is
shown in Fig. 7b. One may observe the complete crystallization of the
may notice the different shape of the protrusions formed during the UW interfacial zone. An interesting feature is that the welding energy re-
process in the HAZ with the increase in thermal energies. For sample sponsible to produce a sound HAZ with no detectable crystallization
S6, the higher deformation is attributed to excessive viscous flow in the (S3) is somewhat close to the energies of samples that show lack of
supercooled liquid state. In addition, it is clear to observe the greater joining and an amorphous HAZ (S1) to those samples (S4, S5, S6) that
surface oxidation with the increase in thermal energy. This is due to the crystalline compounds formed in the HAZ. This demonstrates that the
diffusion temperature dependence of oxygen in the metal surface. welding parameters have a very narrow range for setup, even though
Fig. 5 shows the diffraction patterns of samples, S3, S5, and S7. the supercooled liquid window is 66 °C.
From the diffraction patterns, it is distinct to observe the evolution of To assess the mechanical response of the welded samples, Vickers
crystallization in the HAZ with the increase in thermal energy. For microhardness was performed along the HAZ of welded samples. As can
sample S3, only a broad and diffuse peak is seen confirming the be seen in Fig. 8, the hardness of samples where no crystallization in the
amorphous nature of the joints. For sample S5, diffraction peaks are of interface was detected (S1 and S3) remains relatively, within the
the NiZr2 “big cube” phase, which are in accordance with the results measured error, equal to the non-heat-affected zone (positions −1,
found by Kuroda et al. (2009) for resistance welding of a Zr-based BMG. 1 mm). A small increment in hardness at the interface position may be
In addition to crystalline peaks, a discrete diffuse and broad peak is yet due to the formation of nanocrystals with a typical size of 5–20 nm. This
present representing the amorphous phase. For sample S7, peaks of phenomenon has been previously reported after annealing of Zr-based
crystalline compounds are evident for the CuZr2 tetragonal phase. Ac- BMGs (Fan and Inoue, 2000). Crystals with this grain size were not
cording to Wang et al. (2000), “despite the complexity of different detected neither by XRD nor by SEM analysis, for samples S1, S2, and
crystallization paths, the main final crystallized product in Zr-based S3. With the increase in welding energy and a large decrease in the Vf
BMGs is Zr2Cu”. Baricco et al. (2001) have noticed a similar crystal- (Fig. 6), the hardness in the HAZ increases dramatically. The crystalline
lization behavior during thermal annealing of a Zr-based BMG at compounds formed during the devitrification of Zr-based BMGs have
superior hardness compared to the amorphous phase, however, with a

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A.F. Andreoli et al. Journal of Materials Processing Tech. 255 (2018) 760–764

Fig. 4. Outer appearance of samples S3 (3770 J) and S6 (5960 J) after

the resistance upset welding process with different parameters setup.

Table 3
Thermal data acquired using a thermal imaging camera during the UW process for S3, S4,
S5 and S6 samples.

Sample Tp (°C) Time above Tx (ms) Heating rate (°C/s) Cooling rate (°C/s)

S3 456.3 0 336.7 55.6

S4 422.8 0 183.2 37.0
S5 492.0 530 314.5 73.7
S6 475.2 770 215.5 52.5

Fig. 6. The amorphous phase volume fraction of samples S1, S3, S4, S5 and S7 after the
resistance upset welding process. The joining interface stands for position 0 mm.
Fig. 5. XRD patterns of the HAZ for samples S3, S5, and S7. The XRD patterns represent a
0.6 × 0.6 mm X-ray beam at the weld interface.

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A.F. Andreoli et al. Journal of Materials Processing Tech. 255 (2018) 760–764

Fig. 7. (a) Secondary electron mode (SE) SEM image of sample S1 evidencing a lack of joining in the interface. (b) Interfacial zone of sample S5 where crystallization occurred during the
welding procedure (SE SEM image).

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