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Scripta Materialia 62 (2010) 945–948

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The role of wettability in metal–ceramic joining

K. Nogi*
Hosokawa Micron Corporation, 9, 1-Chome, Shoudai Tajika, Hirakata-shi, Osaka 573-1132, Japan
Received 20 January 2010; revised 1 March 2010; accepted 2 March 2010
Available online 4 March 2010

Abstract—The effects of oxygen, applied DC voltage and surface orientation on the wettability of ceramics by liquid metals are clarified
and new methods for metal–ceramic joining are proposed based on information from wetting experiments, using three examples. The
strengths of Ni–Al2O3 joints obtained at very low oxygen potentials are higher than in high oxygen potential environments. Applying a
DC voltage to the interface between metals and partially stabilized zirconia is shown to improve the strength of metal–zirconia joints.
Cu and SiC can be strongly joined without using active elements such as Ti and Zr by controlling the joining conditions.
Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Wettability; Contact angle; Joining; Liquid metal

It is well known that the wettability of solid metals
and ceramics by liquid metals plays an important role in
many materials processes. Examples include the refining
of liquid metals, the production of metal–ceramic com-
posites, and nearly all soldering and brazing processes
by which a metal is joined to another metal or a ceramic.
As the wettability is affected by many factors, such as
atmosphere, temperature, thermodynamic stability of li-
quid and solid, alloying constituents, and the surface con-
dition of the solid (surface roughness, surface stress and
crystallographic orientation), it is possible to obtain
high-quality materials and also high-quality joints by
controlling the wettability. Accordingly, much research
on the vapour/liquid/solid triple lines that underlie wet-
ting by metals has been conducted by many researchers
on a number of systems [1–15].
If the coefficients of thermal expansion of metal and
ceramic are the same and no brittle reaction product is
formed at the metal–ceramic interface, better wettability
results in higher joining strength between metal and cera-
mic. Unfortunately, the coefficients of thermal expansion
of metals are usually much larger than those of ceramics.
Furthermore, good wettability of solids by molten metals
is often accompanied by the formation of brittle interme-
tallic compounds. Joining processes are, therefore, com-
plex; this paper reviews the wettability of ceramics by
liquid metals in the context of joining, and proposes
* Tel.: +81 72 855 2307; fax: +81 72 855 2561; e-mail: knogi@hmc.
hosokawa.com
new methods for metal–ceramic joining mainly based
on studies of the underlying capillary phenomena.
The temperature dependence of contact angles be-
tween liquid pure Al and Al2O3 has been reported by
many researchers. The obtained results, however, show
large variation in the contact angles reported. For exam-
ple, the largest and smallest contact angles are 130°
and 50°, respectively, at 1273 K with many other val-
ues located in between.
An interesting result was obtained by Hausner [16] in
the liquid pure Al and Al2O3 system. He investigated con-
tact angles under changing oxygen potential in a gaseous
atmosphere and found that large contact angles (180°)
can be obtained at high oxygen potential (1010 Pa) and
small values (90°) at low oxygen potential (1050 Pa) at
973 K. The results suggest that it is possible to control
the contact angles of liquid Al on Al2O3 by changing
the oxygen potential of the process atmosphere. Further-
more, this tendency should be observable in other liquid
metals whose oxygen solubility is very low and also those
whose oxide is thermodynamically stable and rigid, when
these are in contact with solid oxides.
On the other hand, it has been observed that the effect
of oxygen in liquid metal on the contact angle between
liquid metals such as Fe and Ni and thermodynamically
stable ceramics shows a different behavior. The contact
angles between liquid Ni and Fe and Al2O3 show maxi-
mum values at certain amounts of oxygen content in li-
quid Ni and Fe [17,18].
The work of adhesion, Wad, can be expressed by the
following equation:

1359-6462/$ - see front matter Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2010.03.007
946 K. Nogi / Scripta Materialia 62 (2010) 945–948

W ad ¼ cð1 þ cos hÞ; ð1Þ mic if the ceramic has an ionic oxygen character, e.g.
where c and h are, respectively, the surface tension of li- partially stabilized zirconia (PSZ) [20,21].
quid metal and the contact angle between liquid metal When oxygen is removed from the liquid metal–PSZ
and Al2O3, respectively. interface, dissociation of PSZ occurs and both oxygen
It is well known that oxygen acts as a surface active and zirconium dissolve into the liquid metal. On the
element which reduces the surface tension of liquid met- other hand, when oxygen is supplied to the liquid me-
als. Accordingly, a large value of the work of adhesion tal–PSZ interface, the liquid metal at the interface is oxi-
can be expected at very low oxygen levels where large dized and liquid metal oxide penetrates into the PSZ
surface tension and small contact angles are attained. grain boundary.
It has been reported that the work of adhesion at low As shown in Figure 2, it is possible to control the con-
levels of oxygen is two times larger than that at high lev- tact angle between liquid Cu and PSZ. By changing the
els of oxygen [17]. direction of the DC current, it is possible to supply and
In the case of the liquid metal/Al2O3 system, the fol- remove oxygen to and from the interface between liquid
lowing reaction occurs at the interface between the li- Cu and PSZ. As shown in Figure 3, solid phase can be
quid metal and Al2O3: observed at the liquid Cu surface when a DC voltage
is supplied to remove oxygen from the interface. The so-
Al2 O3 ¼ 2Al ðin liquid metalÞ þ 3O ðin liquid metalÞ lid phase was confirmed to be ZrO2 by electron micro-
probe analysis (EPMA). Supplying oxygen to the
ð2Þ
interface is also an effective way to decrease the contact
Reaction (2) proceeds easily under low oxygen poten- angle. In this case, it is confirmed that Cu penetrates
tial in an atmosphere since oxygen is easily released from ZrO2 along grain boundaries, probably as Cu oxide.
the liquid metal to the atmosphere. Joining condition and the joining strength as mea-
In fact, it has been revealed that the interface between sured by the four-point bending test are summarized
Ni and Al2O3 is roughened by reaction (2) especially at
the Al2O3 grain boundary [17]. This result implies that it
is possible to join Ni and Al2O3 under a very low oxygen
potential by improving the wettability and using a
roughened interface which yields an anchor effect. The
dissociation of Al2O3 into Al and O shown by reaction
(2) occurs not only in liquid Ni but also in solid Ni; li-
quid Ni and solid Ni differ only in terms of their disso-
ciation rate. It is reasonable to consider that the
diffusivity of Al and O from the interface between
Al2O3 and solid Ni into solid Ni is relatively slower than
into liquid Ni. Figure 2. Change in contact angle between liquid Cu and ZrO2 at
Solid Ni and Al2O3 were joined in a purified hydro- 1423 K. Applied current: 0.1 A; applied charge: 6 C.
gen atmosphere by applying a load to ensure contact be-
tween Ni and Al2O3 [19]. Figure 1 shows the effect of
temperature and bonding time on the bonding strength
of the Ni and Al2O3 joint. It is clear from Figure 1 that
the bonding strength increases with temperature. The
maximum bonding strength, as measured by four-point
bending tests, is on the other hand observed at 3.6 ks.
When a sample is kept for 360 ks, the bonding strength
cannot be measured since the sample fractures in the
vicinity of the interface because of the stress concentra-
tion caused by the difference in the coefficient of thermal
expansion between Ni and Al2O3.
Wettability can be also controlled by applying a DC
voltage at the interface between liquid metal and cera-

Figure 1. Effects of temperature and bonding time on the bonding Figure 3. SEM and X-ray images at the Cu droplet surface after 3.6 ks
strength of a Ni–Al2O3 joint. at 1423 K: (a) SEM, (b) Zr image, and (c) O image.
 K. Nogi / Scripta Materialia 62 (2010) 945–948
Table 1. Joining condition and joining strength of Fe–ZrO2 joint at
1723 K.
ZrO2 Quantity (C) Strength (MPa) Fractured place
15 M 630 30 ZrO2 bulk
15 M 18 94 ZrO2 bulk
8Y 100 16 ZrO2 bulk
8Y 50 15 ZrO2 bulk
8Y 6 9 Interface
15 M, 15 mol% MgO; 8Y, 8 mol% Y2O3.
in Table 1. The scatter in the joining strength values in
Table 1 can be attributed to a difference in joined area
at the Fe–ZrO2 interface, since the joining was con-
ducted without a load [22]. The joining strength of sam-
ples to which a DC voltage was applied, however, is
about eight times larger than that produced when no
DC voltage is applied to the sample. This means that
applying voltage to remove oxygen from the interface
is an effective way to improve the joining strength. Fur-
thermore, it indicates that the nature of the ZrO2 and
the quantity of electricity applied are important factors
affecting the joining strength. Consequently, further
experiments should be performed to obtain the optimum
conditions to maximize joining strength.
Figure 4 shows EPMA results of the interface be-
tween Cu and ZrO2. It can be seen from Figure 4 that
ZrO2 particles disappear and an alloy phase of Cu and
Zr is formed at the interface between Cu and ZrO2; an
anchor effect of the alloy phase along the grain bound-
ary of ZrO2 can also be seen. These results correspond
well with those in the wetting experiment.
PSZ is sometimes used as a thermal barrier coating
because of its excellent thermal properties. The coating
is usually obtained by thermal spraying. One of the
problems of coatings produced by thermal spraying is
that it is difficult to obtain a sufficient joining strength
between PSZ and bulk metal; to date, no method has
been proposed to improve the joining strength after
thermal spraying. To this end, applying the DC voltage
method might be a strong candidate for improving the
interface characteristics between PSZ and bulk metal
since this method can control the interface from the out-
side. The effect of applied DC voltage on the joining
strength of a thermal spray coating of PSZ on Fe was
investigated. The joining strength between thermal
spray-coated PSZ and Fe substrates was evaluated by
dropping a steel ball (5.48 g, 11 mm in diameter) onto
the sprayed PSZ from a height of 1 m. The results are
Figure 4. SEM and X-ray images at the Cu–ZrO2 interface after bonding test: (a) SEM, (b) Zr image, and (c) Cu image.
947
summarized in Tables 2 and 3 [21]. The results in Table
2 were obtained by applying a DC voltage to supply
oxygen to the interface between Fe and PSZ. The results
in Table 3, however, were obtained by applying a volt-
age to supply oxygen, and then removing oxygen from
the interface. The experimental temperature, 1673 K,
was selected based on consideration of the melting tem-
perature of FeO, 1650 K, since liquid FeO easily reacts
with PSZ and also penetrates into the grain boundary
of PSZ. Although the optimum condition for joining is
not clear from Tables 2 and 3, it is obvious that the join-
ing strength is affected by applying a voltage. Accord-
ingly, further investigation is required to obtain
reliable metal–PSZ joining.
Single-crystalline SiC is a promising semiconductor
for high-temperature use. SiC needs to be joined with
a metal if it is to be used as a semiconductor. It has been
reported that characteristic wetting, which reflects an
influence of the surface orientation of SiC, is observed
in the liquid Cu and SiC system at low temperature
and high vacuum [23]. It has been clarified that the
mechanism of a hexagonal wetting is mainly caused by
the low solubility of C and the similarity of the lattice
constants of Cu and SiC [24].
Successful joining of SiC to metal was only achieved
by Cu. When metals such as Fe and Ni dissolve both C
and Si, a violent reaction between the metals and SiC
was observed and cracking was observed at the inter-
face. It might be possible to form a Cu electrode on
SiC by evaporation of Cu on SiC and heat treating just
below the melting point of Cu.
The tensile strength of Cu–SiC single-crystal joints at
room temperature is shown in Table 4. Three joints were
measured at each holding time. It was found that high
tensile strength can be obtained for short holding times,
and the samples held for longer were fractured at the
interface between Cu and SiC single crystal before these
could be subjected to tensile strength testing.
Table 2. Experimental conditions and results of joining strength of
sprayed PSZ on iron.
Experimental conditions Results
Temp. (K) Quantity (C) Time (s) Strength (cycles)
1673 0 5100 NJ
1673 15 75 NJ
1673 100 500 >400
1673 1000 5000 NJ
948 K. Nogi / Scripta Materialia 62 (2010) 945–948

Table 3. Experimental conditions and results of joining strength of sprayed PSZ on iron.
I II Strength
Temp. (K) Quantity (C) Time (s) Temp. (K) Quantity (C) Time (s) (cycles)
1673 0 5100 Not treated N.J.
1673 100 500 1673 500 2500 N.J.
1673 100 500 1573 500 2500 >400
N.J., not joined.

Table 4. Tensile strength of Cu/SiC single crystal joined at 1371 K. [8] P. Shen, H. Fujii, Kiyoshi Nogi, Scripta Mater. 52 (2005)
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