Vacuum 114 (2015) 58e65

Contents lists available at ScienceDirect

Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Microstructure and mechanical properties of W/Cu vacuum diffusion

bonding joints using amorphous FeeW alloy as interlayer
Song Wang a, b, Yunhan Ling b, *, Jianjun Wang a, Guiying Xu a
a
b

Laboratory of Special Ceramics and Powder Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
Laboratory of Advanced Materials, Tsinghua University, Beijing 100084, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 29 September 2014
Received in revised form
5 January 2015
Accepted 7 January 2015
Available online 14 January 2015

W/Cu Functionally Graded Materials (FGM) are promising materials to be used as plasma facing materials
(PFM) for a fusion reactor as well as a heat sink material for high power microelectronic devices. The
immiscible properties in W and Cu, however, make it difcult to join each other without introduction of
active metals like iron group elements. In this paper, pulse electro-deposited FeeW amorphous alloy
forming on a copper sheet was proposed as interlayer to join W and Cu via vacuum diffusion bonding. It
was found that an improvement in bonding strength and a decrease in bonding residual stresses was
obtained by the bidirectional diffusion of Fe, in the form of highly active amorphous state, in W and Cu at
the weld temperature. The diffusion transition regions were formed near the W/Cu interface which is
consisted of a solid solution zone and various phases between the FeeW and FeeCu binary systems and
two different fracture phenomena was observed on the basis of the microstructural characteristics. With
the introduction of this new kind amorphous coating as interlayer, the vacuum diffusion bonding joint of
W and Cu heating at 950
C for an hour with a load of 30 MPa showed a maximum tensile strength of
about 146 MPa.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Vacuum diffusion bonding
Amorphous interlayer
Microstructure
Tensile strength test
Fracture mechanism

1. Introduction
The refractory metal tungsten is recommended as the leading
candidate for the divertor section of the International Thermonuclear Experimental Reactor (ITER) because of many favorable
properties such as high melting point, high sputtering threshold,
high thermal conductivity and a low coefcient of thermal expansion [1e5], and copper has been proposed as the heat sink material
behind the plasma facing materials (PFM) due to its high thermal
conductivity, high electrical conductivity and high ductility [6,7].
However, the large difference in melting point and coefcient of
thermal expansion between these two metals makes it very difcult to join them together.
Several methods have been developed to fabricate W/Cu Functionally Graded Materials (FGM), such as hot isostatic pressing
(HIP) bonding [7], diffusion bonding [8], powder metallurgy [9e11],
Vacuum plasma spraying [12], mechano-chemical progress [13],
inltration process [14], direct metal laser sintering [15,16], eld-

* Corresponding author. Tel.: 86 010 62772856.

E-mail address: yhling@mail.tsinghua.edu.cn (Y. Ling).
http://dx.doi.org/10.1016/j.vacuum.2015.01.008
0042-207X/ 2015 Elsevier Ltd. All rights reserved.

assisted sintering [17], etc. Braze welding is also an effective

method to fabricate W/Cu FGM. The use of CuMn base brazing alloy
demonstrated a good tensile strength of joint ~200 MPa with failure
in the Cu alloy near the brazed joint, the high temperature brazing
however is not compliant with ITER new specications [18e20].
Plasma spraying is another promising method to fabricate W/Cu
FGM. Tungsten has been successfully plasma sprayed onto oxygenfree copper in thicknesses up to 1 mm under inert gas protection
[21]. The intrinsic limitation of this technique is the contamination
of oxygen and carbon due to higher level of oxygen at 0.2% has been
found in those coatings.
One of the most important methods for bulk material fabrication is powder metallurgy. However because the WeCu system
exhibits mutual insolubility or negligible solubility, WeCu powder compacts show very poor sinterability, even by liquid phase
sintering above the melting point of the Cu phase. Although
every method has its own merits, the interface compatibility,
however, is still the core issue challenging the existing processes.
Although the common welding defects such as cracking and
distortion can be avoided through diffusion bonding technology
[22,23], the application of conventional fusion welding to join the

S. Wang et al. / Vacuum 114 (2015) 58e65

59

previous works [24,25], the effect of the amorphous FeeW

coating transformation from non-crystal to crystal on WeCu
composite materials was studied in detail. During the bonding
process, the FeeW deposit undergoes a change from the amorphous to nano crystals of alloy compounds with grain sizes of
58.6 nm, 26.3 nm for W and Fe2W, respectively. In the current
research, the effect of bonding temperatures on the microstructure and mechanical properties of the joint interfaces were
studied extensively.

2. Experimental details
2.1. Electrodeposition of amorphous FeeW coatings on Cu

Fig. 1. Heating curve for tungsten and copper bonding.

dissimilar alloys is not feasible because of the large difference in

the melting points between these alloys. In this study, the possibility of fabricating W/Cu FGM with a new kind of amorphous
FeeW coatings electrodeposited onto the Cu foils by vacuum
diffusion bonding (VDB) is explored. A Cu foil with thickness of
30 mm was used as an interlayer and the effect of bonding temperatures on the microstructural developments across the joint
and the resulting mechanical properties was investigated. In the

FeeW amorphous alloys were electroplated using an aqueous

solution containing 0.212e0.243 mol L1 ferrous sulfate heptahydrate, 0.018e0.036 mol L1 sodium tungstate dehydrate and
0.26 M ammonium tartrate. Tartaric acid complex system was
selected as the complex agent in the study. A pH value of 8.0 was
maintained by adding either ammonia or dilute sulfuric acid. For
every electroplating, the current density was set to be
0.05 A cm2 and the plating temperature as 60
C, while the time
was xed to 8 min. Amorphous FeeW coatings were prepared by
electroplating onto the surface of Cu foils. Cu foil is chosen as the
substrate because of its high thermal conductivity and excellent
plasticity. Before deposition, the Cu foil sample was electrochemically polished with phosphoric acid, washed by distilled

Fig. 2. (a) XRD pattern for FeeW coating; (b) TEM selected area diffraction pattern for FeeW coating.

Fig. 3. (a) SEM top view morphology of as-deposited FeeW coating; (b) Cross-section morphology.

60

S. Wang et al. / Vacuum 114 (2015) 58e65

Fig. 4. (a) The line scan map of VDB interface between W and Cu bonded at 900
C; (b) the curve of diffusion depth prole at 900
C.

water and then immersed in the bath as a cathode, in the meantime the inert graphite was selected as the counterpart anode.

3. Results and discussion

3.1. Structure and surface morphology of the coatings

2.2. Diffusion bonding using amorphous FeeW coating as an

interlayer
The coated samples were transferred to the diffusion bonding
chamber and the amorphous FeeW interlayer was placed between
the surfaces of W and Cu. Then they were bonded under different
VDB conditions in a ZTY-50e23 vacuum hot pressing furnace
(104e103 Pa). The load used in this investigation was 30 MPa for
all joints. The isothermal bonding temperatures were designed to
be 850
C, 900
C and 950
C, respectively. Fig. 1 showed the
temperature schedule, the bonding duration was xed to 60 min at
each welding temperature.
To evaluate the bonding performance of the joint specimens,
tensile strength tests were employed using a DWD-200D universal
testing machine. The microstructures of the specimens were
examined using a eld emission scanning electron microscope
(FESEM, HITACH S4800) equipped with an Oxford energy dispersive spectrometer (EDS). X-ray diffraction (XRD, D/max 2500, CuKa) analysis was conducted on the samples to determine the
crystallinity of the deposited and bonded surfaces, while the
amorphous as-deposited alloy sample was observed by transmission electron microscopy (TEM, JEM-2010F).

The X-ray diffraction pattern of the FeeW coating electrodeposited at 0.05 A cm2 is presented in Fig. 2(a). Only one broaden
peak is found at the angle of approximately 42
, implying that the
as-deposited lm was amorphous. Fig. 2(b) showed the TEM
morphology and the selected area electron diffraction pattern of
the FeeW coating. The concentric aureole of transmission electron
microscope further demonstrated that the FeeW coating is a kind
of amorphous material.
The SEM morphology of the FeeW coating was depicted in
Fig. 3(a). Compact and smooth FeeW coating was successfully obtained by electroplating, and the content of tungsten varies from 22
to 30 at% depending on the cathodic current density applied.
Fig. 3(b) displayed the cross-section prole of the amorphous
FeeW coating, it can be seen that the thickness of the coating is
2.5 0.05 mm under the given plating conditions.
3.2. Interfacial structure of the W/Cu composite
The bonding temperature is important in determination the
formation of reaction phases involving elemental diffusion. The
melting point of copper is 1083
C, which is much lower than

S. Wang et al. / Vacuum 114 (2015) 58e65

61

Fig. 5. (a) The line scan map of VDB interface between W and Cu bonded at 950
C; (b) the curve of diffusion depth prole at 950
C.

that of tungsten (3400
C), three temperature scenarios below

copper's melting point was planned to investigate the diffusion
bonding behavior. Needless to say that the interlayer's crystal
size and elementary composition will change as a function of
the experimental bonding parameters such as holding time,
temperature and the pressure applied during the bonding
processes.
The amorphous FeeW coating has a high adhesive and
joining activity on W and Cu, as seen from Figs. 4 and 5 a tight
junction between the two contact surfaces is formed successfully. Figs. 4(a) and 5(a) presented the line scan map of the VDB
interface between W and Cu. The interdiffusion of iron element
was found on both sides of tungsten and copper foil. The results
suggest that Fe in the coating diffused into both W and Cu
substrates. From Fig. 4(b), the Fe diffusion depth is calculated to
be about 1.2 mm on the side of tungsten and about 6.6 mm on the
copper side at 900
C. While at 950
C, the diffusion depth of Fe
atom is measured to be about 1.5 mm on the tungsten side, and
about 7.25 mm on the copper side, as shown in Fig. 5(b), suggesting that Cu dissolves in the solid solution of a-Fe and Fe is
soluble in Cu solid solution likewise. It should be mentioned
that Fe and W atoms are inclined to form intermetallic compounds as Fe2W phase and Fe7W6 phase (Fig. 6) once beyond its

solubility limit. One reason for that might be the iron atomic
diffusive rate in W is much lower than that in copper. The
melting point difference is also a probable factor determining
the diffusive behaviors. Figs. 4 and 5 revealed that the diffusion
depth of Fe atom at 950
C is deeper than that at 900
C. Higher
diffusion temperature promotes a good plastic deformation capacity for copper, resulting in better tightness of the connecting
surface. The joint (under optimization bonding conditions) between W, FeeW interlayer and Cu is achieved when interdiffusion between the materials is present without the formation of voids and brittle phases such as Fe2W intermetallic
compounds. The new phases were produced during the
bonding, which would control the ultimate mechanical
properties.
3.3. Tensile strength test
Tensile strength performance further conrms the successful
jointing of W and Cu. The results of tensile strength tests on W and
Cu alloys are listed in Table 1.
As seen, the diffusion joints heated at 900
C and 950
C for a
duration of 60 min is more successful as they are higher in tensile
strength than those of joints obtained at 850
C. During the

62

S. Wang et al. / Vacuum 114 (2015) 58e65

Table 1
Results of tensile strength test on W and Cu alloys.

Fig. 6. (a) XRD pattern of the interlayer after heat treatment at 950
C-60 min; (b) The
phase constitution.

Joint isothermal conditions

s(MPa)

Fracture location

850
Ce60 min

900
Ce60 min
950
Ce60 min

15
142
146

Cu foil/Cu
Interface W side
Interface W side

bonding diffusion the atoms on both contact surfaces diffuse and

some intermetallic compounds (Fe2W and Fe7W6) will be formed
and could improve the bonding strength at a certain range and to
certain extent. At 850
C the fracture location was the interface of
Cu foil and Cu, implying that the interlayer cannot joint well with
Cu for the bonding temperature was too low. At 900
C and
950
C the fracture locations were both at the interface W sides.
The surface of W might be weakened during the hot-press process and the weakened area might inuence the residual stresses
[7]. From the fractographic analysis of surfaces obtained after
tensile strength testing, the fracture mechanisms can be discerned by the microstructural characteristics of each interface
formed by diffusion (seen from Figs. 7 and 8). Figs. 7 and 8
demonstrated the fracture surface morphology of FeeW interlayer of a joint W/Cu obtained at 900
C and 60 min and the EDS
element mapping of the fracture surface. Figs. 7 and 8 demonstrated the fracture surface morphology of FeeW interlayer of a
joint W/Cu obtained at 900
C and 60 min and the EDS element
mapping of the fracture surface, while Fig. 9 described the fracture surface morphology of FeeW interlayer of a joint W/Cu
obtained at 950
C and 60 min and the EDS element mapping of
the fracture surface. The fracture surfaces suggest the various
mechanisms as follows:
At different bonding conditions (900
Ce60 min and
950
Ce60 min), the cracks take place by two different mechanisms: brittle fracture and ductile fracture. The brittle fracture
always occurs through the hard metal W (seen from Figs. 7 and

Fig. 7. Brittle fracture surface of FeeW interlayer of a joint W/Cu, bonded at 900
C for 60 min.

S. Wang et al. / Vacuum 114 (2015) 58e65

63

Fig. 8. (a) Fracture morphology of the interlayer W/Cu, bonded at 950
C for 60 min, A: brittle fracture and B: ductile fracture; EDS element mapping of (b) Cu; (c) Fe; (d) W.

9(a)A), while the brous brittle fracture appears through the

Fe2W and Fe7W6 phases (Figs. 8(a)B and 9(a)A); and the ductile
fracture emerges through the soft metal copper (Figs. 8(a)B and
9(a)C). From the above morphology and element distribution
analysis, it might be concluded that lower temperature (900
C)
is conducive to the diffusion of FeeW (especially for Fe) to W

substrate without inducing much harmful compounds or phase

separation; higher temperature (950
C) enhanced interdiffusion of Fe and W but leading to voids formation and phase
segregation. That how to ameliorate the constitution design of
FeeW amorphous coating to prevent or reduce the formation of
in homogeneous phase await to be further investigation.

Fig. 9. (a) Fracture morphology of the interlayer W/Cu, bonded at 950
C for 60 min, A and B: brittle fracture; C: ductile fracture; EDS element mapping of (b) Cu; (c) Fe; (d) W.

64

S. Wang et al. / Vacuum 114 (2015) 58e65

due to its high diffusion activity. The diffusion transition region

near the W/Cu interface was formed and consisted of a solid solution zone and intermetallic compounds with Fe2W phase and
Fe7W6 phase. The vacuum diffusion bonding joint processed at
950
C for 60 min with a load of 30 MPa showed the maximum
tensile strength of about 146 MPa. In addition, the vacuum diffusion
bonding technique has been successfully employed to prepare
relatively large size W/Cu-PFM specimens.
From the fractographic analysis of surfaces obtained after mechanical testing, fracture mechanisms can be deduced by depending on the microstructural characteristics of the various interfaces
formed by the diffusion bonding. The fracture failures originated
from two different mechanisms: brittle fracture and ductile fracture. More efforts await to be invested in pursuit of higher bonding
between W and Cu via further amelioration of the interface
compatibility.
Acknowledgments
This research was funded by the National Magnetic connement
Fusion Science Program under contract 2010GB106003 and National Basic Research Program of China (973 Program) under grant
No. 2011CB61050, and the NSAF Program (No. U1430118).
References

Fig. 10. Pictures of the vacuum diffusion bonding W/Cu module samples.

W/Cu bulk PFM specimens were successfully prepared by the

VDB technique in this study, as seen from Fig. 10. With the introduction of FeeW amorphous interlay, the size of the specimen can
be enlarged to 100  100 mm, meeting the requirements of the
divertor module's size.
4. Conclusions
Bonding of W and Cu with a novel amorphous FeeW coating as
an interlayer was successfully demonstrated. The amorphous and
nanostructured FeeW has good adhesive strength with substrate

[1] Zhou DH, Liu Y, Chen JL, Zhou ZJ, Yan R. Surface cracking behaviors of ultrane grained tungsten under edge plasma loading in HT-7 tokamak. Plasma
Sci Technol 2013;15:605e8.
[2] Li YG, Zhou WH, Huang LF, Zeng Z, Ju X. Cluster dynamics modeling of
accumulation and diffusion of helium in neutron irradiated tungsten. J Nucl
Mater 2012;431:26e32.
[3] Loarte A. Power and particle control. Nucl Fusion 2007;47:S203e63.
[4] Mayer M, Andrzejczuk M, Dux R, Fortuna-Zalesna E, Hakola A, Koivuranta S.
Tungsten erosion and redeposition in all-tungsten divertor of ASDEX upgrade.
Phys Scr 2009;T138:014039e45.
[5] Mayer M, Likonen J, Coad JP, Maier H, Balden M, Lindig S. Tungsten erosion in
the outer divertor of JET. J Nucl Mater 2007;363e365:101e6.
[6] Mitteau R, Missiaen JM, Brustolin P, Ozer O, Durocher A, Ruset C. Recent developments toward the use of tungsten as armour material in plasma facing
components. Fusion Eng Des 2007;82:1700e5.
[7] Saito S, Fukaya K, Ishiyama S, Saito K. Mechanical propertied of HIP bonded W
and Cu-alloys joint for plasma facing components. J Nucl Mater
2002;307e311:1542e6.
[8] Wang CB, Shen Q, Zhou ZG, Zhang LM. Diffusion welding of 93W alloy to OFC
and structural control of 93W/OFC joint. J Mater Sci 2005;40:2105e7.
[9] Gan KK, Chen N, Wang Y, Gu MY. SiC/Cu composites with tungsten coating
prepared by power metallurgy. Mater Sci Technol 2007;23:119e22.
[10] Ryu SS, Kim YD, Moon IH. Dilatometric analysis on the sintering behavior of
nanocrystalline WeCu prepared by mechanical alloying. J Alloys Compd
2002;335:233e40.
[11] Hashempour M, Razavizadeh H, Rezaie HR, Salehi MT. Thermochemical
preparation of We25%Cu nanocomposite powder through a CVT mechanism.
Mater Charact 2009;60:1232e40.
[12] Pintsuk G, Smid I, Doring JE, Hohenauer W, Linle J. Fabrication and characterization of vacuum plasma sprayed W/Cu-composites for extreme thermal
conditions. J Mater Sci 2007;42:30e9.
[13] Cheng JG, Song P, Gong YF, Cai YB, Xia YH. Fabrication and characterization of
We15Cu composite powders by a novel mechano-chemical process. Mater Sci
Eng A 2008;488:453e7.
[14] Yang XH, Zou JT, Xiao P, Wang XH. Vacuum 2014;106:16e20.
[15] Gu DD, Shen YF. Inuence of Cu-liquid content on densication and microstructure of direct laser sintered submicron WeCu/micron Cu powder
mixture. Mater Sci Eng A 2008;489:169e77.
[16] Chen PG, Luo GQ, Shen Q, Li MJ, Zhang LM. Thermal and electrical properties
of WeCu composite produced by activated sintering. Mater Des 2013;46:
101e5.
[17] Rape A, Chanthapan S, Singh J, Kulkarni A. Engineered chemistry of CueW
composites sintered by eld-assisted sintering technology for heat sink applications. J Mater Sci 2011;46:94e100.

[18] Barabash V, Akiba M, Cardella A, Mazul I, Odegard Jr BC, PloEchl
L. Armor and
heat sink materials joining technologies development for ITER plasma facing
components. J Nucl Mater 2000;283e287:1248e52.
[19] Prokoev YG, Barabash VR, Khorunov VF, Maksimova SV, Gervash AA,
Fabritsiev SA. Some problems of brazing technology for the divertor plate
manufacturing. J Nucl Mater 1992;191e194(Part A):483e7.

S. Wang et al. / Vacuum 114 (2015) 58e65

[20] Singh KP, Pandya SP, Khirwadkar SS, Patel Alpesh, Patil Y, Buch JJU. Prequalication of brazed plasma facing components of divertor target elements
for ITER like tokamak application. Fusion Eng Des 2011;86:1741e4.
[21] Zhou ZJ, Song SX, Yao WZ, Pintsuk G, Linke J, Guo SQ. Fabrication of thick W
coatings by atmospheric plasma spraying and their transient high heat
loading performance. Fusion Eng Des 2010;85:1720e3.
mez de Salazar JM, Merino N, Matesanz L. Characterization of
[22] Barrena MI, Go
WCeCo/Ti6Al4V diffusion bonding joints using Ag as interlayer. Mater Charact
2008;59:1407e11.

65

[23] Sabetghadam H, Zarei Hanzaki A, Araee A. Diffusion bonding of 410

stainless steel to copper using a nickel interlayer. Mater Charact 2010;61:
626e34.
[24] Wang S, Ling YH, Zhao P, Zang NZ, Wang JJ, Guo SB. Bonding tungsten, WeCualloy and copper with amorphous FeeW alloy transition. Fusion Eng Des
2013;88:248e52.
[25] Zhao P, Wang S, Guo SB, Chen YX, Ling YH, Li JT. Bonding W and WeCu
composite with WeFe coated copper foil through hot pressing method. Mater
Des 2012;42:21e4.