Materials Characterization 131 (2017) 316–323

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Interfacial characterization in the brazing of silicon nitride to niobium MARK

joining using a double interlayer
M. Morales-Péreza,⁎, L. Ceja-Cárdenasa,b
a
Ingeniería Mecánica, Instituto Tecnológico de Morelia, Av. Tecnológico No. 1500, Col. Lomas de Santiaguito, C.P. 58120 Morelia, Mich., Mexico
b
Doctorado en Ciencias en Ingeniería, Instituto Tecnológico de Morelia, Av. Tecnológico No.1500, Col. Lomas de Santiaguito, C.P. 58120 Morelia, Mich., Mexico

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

Keywords: Both the wetting and adherence of a metal foil interlayer used to join ceramics to metals have a direct effect on
Brazing the interface formation during the brazing process. Sometimes, double interlayers are used to improve the
Ceramic-metal interface strength of the joints and to reduce the stress resulting from the difference between the thermal expansion
Silicon nitride coefficients of the base materials. In this study, we investigated the brazing of silicon nitride, Si3N4 (ceramic
material) to Nb (refractory metal) using a double interlayer. In order to understand the interfacial behavior of
the Si3N4/Nb joint, cylindrical samples of Si3N4 with relative densities of 94.2% and 84.7% were used.
Sandwich-like samples of Si3N4/Ag–Cu/Cu–Zn/Nb were joined at temperatures from 1000 °C to 1100 °C using
different holding times under an inert atmosphere (argon). Analysis by field emission scanning electron mi-
croscopy (FESEM) revealed that the diffusion rate of silicon and the higher porosity of the ceramic specimen
improved the spreading of the liquid metal through the interface at a lower joining temperature. Nb–Si com-
pounds were observed on the nearby niobium substrate when a large dense ceramic was joined at 1100 °C for
20 min. This sample had a chemical composition close to the Nb5Si3 binary phase as confirmed by electron probe
microanalysis (EPMA).

1. Introduction
Silicon nitride (Si3N4) ceramics possess high hardness, low density,
good corrosion resistance, thermal stability and resistance to thermal
shock. These materials are used for high-temperature and corrosive
environments such as in turbochargers and auxiliary power unit com-
ponents for aircraft as reported by Singh et al. [1]. However, it is dif-
ficult to produce complex ceramic shapes with complete densification.
Thus, joining simple ceramic pieces with complex metal components
has become a key technology to overcoming such problems in manu-
facturing. Brazing is among the techniques used to join ceramics to
metals to produce complex components for structural applications, and
it is receiving extensive attention because of its simplicity and cost-
effectiveness [2]. Brazing is a joining process where a filler metal with a
low melting point is heated to form a liquid phase, which is then dis-
tributed between the base materials to be joined. However, there are
two essential issues that remain unsolved. The first is the thermal ex-
pansion mismatch between the ceramic and the metal, which induces
residual stresses during cooling, causing cracks in the joining interface,
as observed by Lemus-Ruiz et al. [3]. Xu and Indacochea [4] studied the
effect of temperature on Si3N4/410-SS assemblies using a Ag–Cu–Ti
filler alloy at temperatures from 840 to 900 °C using different holding
times. The authors observed cracks in the joining interface. They
therefore concluded that the mismatch in the coefficients of thermal
expansion between the base materials and the precipitation of brittle
intermetallic compounds at the bond line led to residual stress forma-
tion on the joining interface. One way to overcome this problem is to
use multiple interlayers with different thermal expansion coefficients,
as reported by Blugan et al. [5]. According to Zhang et al. [6], elements
such as Cu and Zn have been used as soft ductile interlayers to absorb
the residual stresses caused by the thermal expansion mismatch. More
recently, Fernie et al. [7] suggested that a Ag–Cu eutectic alloy is re-
latively ductile and therefore able to produce crack-free joints. The
second issue is the poor wettability of ceramics by non-reactive brazing
filler metals. Do Nascimiento et al. [8] reported that the wetting process
can be either physical or chemical, depending on the nature of the
bonding between the solid and liquid. Physical (non-reactive) wetting
occurs when reversible van der Waals forces act at the interface. León-
Patiño et al. [9] joined a Cu–Al2O3 composite to a Cu substrate using
Cu–Zn and Ag–Cu alloys as filler metals. The authors stated that for-
mation of the joint was promoted by non-reactive wetting in which the
surface roughness present in the Cu–Al2O3 composite improved the

⁎
Corresponding author.
E-mail address: mmoralesp@tecmor.mx (M. Morales-Pérez).

http://dx.doi.org/10.1016/j.matchar.2017.07.026
Received 8 February 2017; Received in revised form 8 July 2017; Accepted 13 July 2017
Available online 13 July 2017
1044-5803/ © 2017 Elsevier Inc. All rights reserved.
M. Morales-Pérez, L. Ceja-Cárdenas Materials Characterization 131 (2017) 316–323

Table 1 Cu70–Zn30 (Johnson Matthey Company, USA) and Ag72–Cu28 (Nilaco

Wetting of silicon nitride by pure metals in high-vacuum atmosphere. Corporation, Japan) foils with thicknesses of 0.025 mm and 0.05 mm,
respectively, were used as the interlayer filler metals. The surfaces of
Liquid metal Temperature (°C) Contact angle (θ) Reference
the samples were ground using a diamond grinding disk, followed by
Cu 1100 133 Sangiorgi et al. [11] final polishing using 3 μm diamond paste. Cleaning was performed in
Cu 1100 131 Ljungbert and Warren [12] an ultrasonic bath with alcohol for 5 min. This methodology was em-
Ag 1100 155
ployed to ensure reproducibility of the surface preparation of the spe-
Cu 1150 135 Nicholas et al. [13]
Ag72-Cu28 900 142 Loehman et al. [14] cimens. The contact surfaces of the niobium and ceramic substrates
Cu 1200 160 Bader et al. [15] were metallized with Cu and Ag, respectively, for 10 min using physical
Ag 1120 110 vapor deposition. Sandwich-like assemblies of Si3N4/Ag72–Cu28/
Cu70–Zn30/Nb were prepared and placed in a graphite die to keep the
joints in close contact during the joining process, as shown in Fig. 1.
capillary effect between the molten filler metal and the solid substrate, The internal walls of the graphite die were coated with boron nitride
which promoted the spreading of the liquid metal. powder (99.5%, pure) to prevent chemical reactions between the
On the other hand, chemical (reactive) wetting occurs when che- carbon and the joining materials. The joining experiments were carried
mical reactions between solids and liquids take place, resulting in out at temperatures ranging from 1000 to 1100 °C using 20, 30, 40, and
strong bonds responsible for wetting [8]. Nomura et al. [10] observed 120 min holding times under an inert atmosphere (argon). The micro-
that the mechanism of reactive wetting consists of dissolution of the structural examination was performed on cross sections of polished
substrate, the diffusion of elements, the formation of the reaction pro- joints. Micrographs of the interfaces were obtained by using a field
duct, and pure wetting. Furthermore, they suggested that this can occur emission scanning electronic microscope (FESEM) equipped with an
in a very small area that is difficult to observe. More recently, Zhang energy dispersive spectrometer (EDS) and electron probe microanalysis
et al. [6] observed this phenomenon in brazing joining of a Si3N4/ (EPMA).
Cu–Zn–Ti/Si3N4 assembly. The authors reported very thin reaction
layers composed by TiN and Ti5Si3 neighboring on the Si3N4 ceramic. 3. Results
Both layers had thicknesses of approximately 1–2 μm.
Numerous studies of non-reactive wetting such as between cop- The influence of the porosity present in the ceramic specimens and
per–silver eutectic alloys and pure metals on Si3N4 [11–15] (Table 1) the effect of the temperature and holding times were the primary
have shown that Cu and Ag do not wet Si3N4 substrates and thus do not parameters analyzed in this study. Table 3 summarizes the results ob-
adhere. However, the weak joining promoted by non-reactive wetting tained for the joining parameters used in the Si3N4/Ag–Cu/Cu–Zn/Nb
can be improved adding an active element (such as Ti, Zr, Hf, In, Nb, assemblies produced by brazing.
etc.,) into the filler metal to destabilize the covalent or ionic bonds of
the ceramic and form an intermediate reaction layer, as reported by 3.1. Si3N4-CS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1000 °C/20 min
Hausner and Wielage [16].
From these works, the basic idea of joining ceramics and metals The cross section of the Si3N4-CS/Ag–Cu/Cu–Zn/Nb assembly
appears to be based on improving the wetting characteristics and joined at 1000 °C for 20 min using the Si3N4 sintered by CS (not shown
forming an interface that can accommodate the difference between the here) revealed a typical non-wetting system in which islands (solid
thermal expansion coefficients of the base materials. However, the drops) formed along the interface. This was probably because the short
specific characteristics of ceramics such as porosity and the use of in- heating time (20 min) resulted in insufficient interfacial energy be-
terlayers also play an important role in the joining process. In the tween the liquid phase (derived from the filler alloys) and the ceramic
present study, we investigated the systematic changes in the interfacial surface. This in turn resulted in insufficient capillary flow, and thus the
behavior of Si3N4/Nb joining as a function of time and temperature liquid film was broken up and islands were formed along the interface,
using a double eutectic filler alloy as the interlayer. as reported by Locatelli et al. [18].

2. Experimental Procedure 3.2. Si3N4-CS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1000 °C/40 min

The silicon nitride ceramics used in this work were produced in our Fig. 2 presents a back-scattered electron scanning micrograph of the
laboratory using α-Si3N4 powder (Toshiba Ceramics Co., Ltd. USA) with Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C for 40 min. As
2.5 and 1.5 wt% of Y2O3 (99.9%, purity) and Al2O3 (99.99%, purity), can be observed from the figure, the double interlayer absorbed the
respectively, as sintering aids. Two kinds of sintering techniques, spark thermal stress, unlike the results reported by Xu and Indacochea [4]
plasma sintering (SPS) and conventional sintering (CS), were used to and Uday et al. [19] for Si3N4/metal joints, which showed cracks at the
produce the Si3N4 substrates to obtain different values of relative edges of the ceramics. Also, the bonding layer exhibited good interac-
density (see Table 2). Additional details of the synthesis and char- tion between the ceramic and metal parts. However, un-joined zones
acterization of Si3N4-SPS are given in a report by Ceja-Cárdenas et al. were observed between the Si3N4-CS and the bonding layer (see “un-
[17]. The ceramic specimens were 5-mm-thick cylinders with diameters joined” zone in Fig. 2).
of 10 mm. The same geometry and dimensions were selected to prepare Numerous studies of wettability have reported that copper and
the Nb (99.98%, Aldrich Chemical Company, Inc., USA) components. silver do not wet Si3N4 substrates, thus forming contact angles higher
than 90° (see Table 1). However, as can be observed from Fig. 2, the
Table 2 sample joined at 1000 °C revealed good wetting of both bonding sur-
Code and sintering conditions of Si3N4 specimens.
faces. In contrast to the samples joined at the same temperature but
Code Sintering conditions Relative density (%) only for 20 min, where a lack of interaction was observed, it is clear
that the longer joining time induced better spreading of the liquid metal
Atmosphere Temperature (°C) Time (min) during the brazing process.
Table 4 shows a quantitative report of the chemical elements con-
Si3N4-CS Nitrogen 1600 60 84.7 ± 1.25
Si3N4-SPS Vacuum 1500 6 94.2 ± 1.65 stituting the points marked in Fig. 2. EPMA analyses revealed small
amounts of silicon dissolved inside the joining interface (Table 4, points
CS: conventional sintering. SPS: spark plasma sintering. 3–6). Silicon should have diffused from the ceramic through the

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Fig. 1. Schematic representation of the sample assembly and

the graphite die used in the joining process.

Table 3 interface because of the decomposition of Si3N4 at high temperatures.

Experimental results for Si3N4/Ag-Cu/Cu–Zn/Nb assemblies. These EPMA results also show that Zn evaporated from the interface
under this joining condition. In other words, the boiling point of Zn is
Code of Si3N4 Assemblies Joining Bonded [●]
specimens parameters
907 °C; thus, at 1000 °C, Zn atoms evaporated almost instantaneously.
Not bonded According to the Cu–Zn phase diagram, it is possible that the Zn gas
[◊] produced was released from the interface, which enabled the bonding
process to be controlled by the transient liquid phase. Similar behavior
Si3N4-CS Si3N4-CS/Ag–Cu/Cu- 1000 °C/20 min ◊
Zn/Nb 1000 °C/40 min ●
was observed by Zhang et al. [20], who reported the evaporation of Zn
1000 °C/120 min ● at 950 °C during the joining of a Si3N4/Cu–Zn–Ti/Si3N4 assembly by
Si3N4-SPS Si3N4-SPS/Ag–Cu/ 1000 °C/40 min ◊ brazing.
Cu-Zn/Nb 1050 °C/20 min ● According to the EPMA results and the micrograph shown in Fig. 2,
1100 °C/20 min ●
it is clear that the spreading of the liquid metal was promoted by non-
The “not bonded” assemblies showed no interaction between the ceramic and metal
reactive wetting. Thus, the active metal, in this case niobium, was not
components (islands), whereas the interaction was complete or partial (un-joined zones) observed to interact with the ceramic to promote reactive wetting.
in the “bonded” assemblies. Landry and Eustathopoulo [21] suggested that in the non-reactive
wetting process, the viscosity and surface tension of the liquid metal
play an important role. León-Patiño et al. [9] stated that increasing the
joining temperature beyond the melting point of the filler alloy im-
proved wetting because it decreases the viscosity and increases the
fluidity of the alloy. On the other hand, the decrease in the surface
tension of the liquid metal can be attributed to the presence of small
amounts of silicon dissolved inside the joining interface (~ 2 wt%), as
shown in the EPMA analyses presented in Table 3. Other studies in the
molten Cu/solid Si system, such as that performed by Protsenko et al.
[22], have shown that the dissolution of silicon improves wetting be-
cause of the decrease in the surface tension of the liquid and because
the surface tension of silicon is lower than that of copper.

3.3. Si3N4-CS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1000 °C/120 min

Fig. 3 presents a back-scattered electron micrograph (center) of the

Si3N4-CS/Ag–Cu/Cu–Zn/Nb specimen brazed at 1000 °C/120 min. No
cracks and interfaces free of discontinuities were found. The scanning
electron micrographs of the cross section of the Si3N4-CS/Ag–Cu/
Fig. 2. Cross-section of the Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C/
Cu–Zn/Nb interfaces (Fig. 3(a) and (b)) revealed good wetting and
40 min.
intimate contact between the substrates and the interfaces. It can be
observed from the figure that at least two phases formed at the inter-
Table 4
EPMA analysis for Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface shown in Fig. 2.
face, namely, discontinuous irregular gray blocks immersed in a clear
solid solution (matrix).
Point Element (wt%) To determine the chemical composition of these regions, EPMA
analyses were performed at different points in the cross section of the
N Si Ag Cu Zn Nb
joint (see Fig. 4 and Table 5). Points 1 and 2 correspond to ceramic
1 59.34 40.66 – – – – (Si3N4), whereas points 3 and 4 are associated with metal (Nb). The
2 – – – – – 100 gray, irregularly shaped blocks (points 5–10) are composed primarily of
3 – 1.99 9.22 88.78 – – copper (~ 91 wt%) with a small fraction of Ag (~ 8 wt%). Points 11–16
4 – 1.69 6.86 91.45 – –
correspond at the silver-rich matrix. According to the Ag–Cu binary
5 – 2.25 9.13 88.62 – –
6 – 2.10 85.74 12.16 – – phase diagram, these phases belong to a Cu-based solid solution (Ag,
Cu) with Ag retained and a Ag-based solid solution (Ag, Cu) with a
composition close to the eutectic point. On the other hand, a high
concentration of niobium (> 10 wt%) was also observed in the area
near the ceramic substrate (points 14–16). It is clear that increasing the

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Fig. 3. (Center) Back-scattered electron micrograph of the Si3N4-CS/Ag–Cu/Cu–Zn/Nb specimen brazed at 1000 °C/120 min. Magnified scanning electron microscopy (SEM) images of
the (a) Si3N4/interface and (b) Nb/interface.

energized to diffuse through the interface and are observed close to the
ceramic zone to form a continuous layer. At this point, we speculate
that the Nb atoms may have rapidly disseminated into the reaction
interface because of the formation of a thin liquid film located between
Si3N4 and Nb, which induced a concentration of Nb immersed in a Ag-
rich solid solution (see Table 5, points 14–16). However, techniques
such as transmission electron microscopy (TEM) are necessary for a
more detailed understanding of the interfacial behavior.
According to the EPMA analyses and the results observed in Fig. 5, it
is clear that the niobium atoms were concentrated where silver atoms
existed, which suggests that niobium atoms could have used the silver-
rich matrix as a transport mechanism to react with the ceramic surface
because of their high chemical affinity with silicon and nitrogen. Then,
wetting and bonding were controlled by the diffusion and dissolution of
niobium, as well as by the chemical reaction promoted at the solid/
liquid/vapor triple line where the wettable reaction product grew
parallel to the liquid/substrate interface. Similar behavior was observed
Fig. 4. Cross-section of the Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C/ by Singh et al. [23], who studied the self-joining of SiC using a Ag–-
120 min. Cu–Ti interlayer. The authors reported that the chemical reaction be-
tween titanium and carbon promoted wetting because of the formation
Table 5 of a thin reaction layer (0.5 μm) composed of stoichiometric carbide
EPMA analyses for Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface shown in Fig. 4.
(TiC).
Point Element (wt%)
3.4. Si3N4-SPS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1000 °C/40 min
N Si Ag Cu Zn Nb

1 63.66 36.34 – – – – Fig. 6 is a magnified view of islands (solid drops) formed in the cross
2 63.40 36.60 – – – – section of the Si3N4-SPS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C
3 – – – – – 100 for 40 min. The interface obtained had behavior similar to that of the
4 – – – – – 100 sample joined at 1000 °C for 20 min (see Section 3.1), where a complete
5 – 1.23 8.09 90.68 – –
6 – – 8.80 91.20 – –
lack of interaction along the borderline between the ceramic and the
7 – – 8.73 91.27 – – metal parts was observed.
8 – – 8.29 91.71 – – Comparing the results shown in Fig. 6 to those shown in Fig. 2.
9 – 1.58 8.96 90.16 – – These samples were joined under the same joining conditions but they
10 – – 8.29 91.71 – –
had different levels of silicon nitride densification (see Table 2). It is
11 – – 70.59 29.41 – –
12 – – 69.59 30.41 – – evident that the Si3N4-SPS specimen was not wetted by the molten filler
13 – – 70.37 29.63 – – alloys. The porosity present in the Si3N4-CS ceramic may have played
14 – 2.33 81.21 5.57 – 10.89 an important role in improving the wetting of Si3N4-SPS. One hypoth-
15 – 2.75 76.78 6.27 – 14.20 esis proposes that the molten filler metal may have infiltrated the sur-
16 – 2.19 81.35 5.57 – 10.89
face porosity, which promoted the spreading of the liquid metal by a
kind of anchoring effect. Some researchers such as Voytovych et al. [24]
joining time caused the diffusion of niobium atoms into the interface. have reported that the phenomenon of “pore closure” observed in
Fig. 5 shows EDS mapping analysis of the elements present in the highly dense ceramics can completely stop infiltration. In this study, the
Si3N4-CS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C/120 min. The Si3N4-CS specimen may have facilitated the infiltration process because
compositional maps show clearly that copper was mainly deposited at it is well known that a greater number of pores, as well as larger pores,
the gray, irregularly shaped blocks, whereas silver was confirmed to be are observed in ceramics with less densification (see Table 2). However,
the major constitutive element of the solid solution (matrix). However, Asthana and Singh [25] reported that in a non-reactive process, spon-
it is interesting to note that the niobium atoms were sufficiently taneous liquid metal infiltration can occur if the capillary pressure at
the pore entrance is negative. This condition is satisfied if the surface

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Fig. 5. EDS mapping of the elements present in the Si3N4-CS/Ag-Cu/Cu–Zn/Nb interface joined at 1000 °C/120 min.

Fig. 6. Cross-section of the Si3N4-SPS/Ag–Cu/Cu–Zn/Nb interface joined at 1000 °C/

40 min. Fig. 7. FE-SEM image of the cross-section of the Si3N4-SPS/Ag–Cu/Cu–Zn/Nb interface
joined at 1050 °C/20 min.
tension and the viscosity of the liquid decreases. As was previously
reported by Protsenko et al. [22], the dissolution of small amounts si- Table 6
licon inside a liquid phase decreases its surface tension. However, in EPMA analyses for Si3N4-SPS/Ag-Cu/Cu–Zn/Nb interface shown in Fig. 7.
contrast to the EPMA analyses shown in Fig. 2 (see also Table 4), the
Point Element (wt%)
EPMA analyses shown in Fig. 6 does not show silicon dissolved at the
interface. Ceja-Cárdenas et al. [26] reported that the larger decom- N Si Ag Cu Zn Nb
position of Si3N4 is closely related to the level of densification reached
in the ceramic. Therefore, the dissolution of silicon, as well as the 1 55.80 44.12 – – – –
2 56.94 43.05 – – – –
porosity present in the Si3N4-CS ceramic, may have improved the
3 – – – – – 100
wetting problems observed when Si3N4-SPS was used under the same 4 – – – – – 100
joining conditions. 5 – – 7.54 92.45 – –
6 – – 7.96 92.03 – –
7 – 1.06 6.33 87.93 – 4.66
3.5. Si3N4-SPS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1050 °C/20 min
8 – 1.38 6.22 89.26 – 3.12
9 – 1.72 7.53 88.47 – 2.21
Fig. 7 shows an FE-SEM image of the Si3N4-SPS/Ag–Cu/Cu–Zn/Nb 10 – 2.68 9.29 88.01 – –
interface obtained after heating the assembly at 1050 °C for 20 min. The 11 – – 91.83 8.16 – –
microstructure observed in the interface is similar to that previously 12 – – 92.43 7.56 – –
13 – – 92.68 7.31 – –
obtained at lower brazing temperatures (Fig. 6). The EPMA analyses 14 – 1.84 87.89 7.06 – 3.19
performed for the sample (see Table 6) revealed clearly the presence of
small amounts of silicon (see points 7–10 and 14) and niobium (see
points 7–9 and 14) dissolved in the area nearby the ceramic substrate.
These results suggest that to achieve the bonding of the highly dense

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Fig. 8. (a) Cross-section of the Si3N4-SPS/Ag-Cu/Cu–Zn/Nb

interface joined at 1100 °C/20 min. (b) Magnified view of
zone A in (a).

silicon nitride (Si3N4-SPS), it was necessary increase the brazing tem-

perature from 1000 to 1050 °C to promote the diffusion and chemical
reaction between the niobium and the ceramic surface. Meanwhile, in
the case of the Si3N4-CS specimens, the porosity may have promoted
wetting at lower temperatures by a non-reactive process.

3.6. Si3N4-SPS/Ag–Cu/Cu–Zn/Nb Interface Joined at 1100 °C/20 min

Fig. 8(a) presents a micrograph of the Si3N4-SPS/Ag–Cu/Cu–Zn/Nb

assembly joined at 1100 °C for 20 min. The interface exhibits a join
without any defects along the borderline between the Si3N4 ceramic
and the niobium substrate. However, a quite uncontrolled reactive zone
was observed between the niobium and the interface (see zone A), in
contrast to the silicon nitride side (see zone B), which exhibited a well-
defined reaction layer. Fig. 8(b) is a magnified view of zone A observed
in Fig. 8(a), which shows the different reaction products that emerged
at this joining temperature.
To determine the chemical composition of these precipitates, EPMA
analyses were performed. Table 7 shows the EPMA results of points 1–6 Fig. 9. High-magnification image of the intermetallic phases that emerged in zone A
in Fig. 9. The microstructure revealed a copper-rich phase (see point 5). shown in Fig. 8(b).

However, it is evident that a type of intermetallic compound emerged in

the joining interface (see points 1–3). These precipitates were com-
posed mainly of Si and Nb, with relatively small amounts of Cu in so-
lution. According to the stoichiometric ratio and the chemical compo-
sition reported by Schlesinger et al. [27], these precipitates can be
attributed to Nb5Si3. Likewise, as can be seen from the Fig. 10, silicon
atoms were concentrated where niobium atoms existed, indicating that
Si may react with Nb to form Si–Nb intermetallic compounds owing to
their strong mutual affinity. Some researchers, such as Schuster et al.
[28], reported thermodynamic analysis of the stability of compounds
that can result from joining Si3N4 to a metal. Lemus and Drew [29]
mentioned that the microstructural evolution and reaction kinetics at
the interface during the joining of Si3N4 to a metal are complicated
because of their dependence on the activities of Si and N2 atoms at the
interface. More recently, Polanco et al. [30] concluded that the free
silicon atoms produced by silicon nitride decomposition can react with
the metallic elements to form different types of metal silicides if the
silicon exceeds the solution limit in the liquid metal. The resultant ni-
trogen can either diffuse into the metal when it has solubility for
Table 7
EPMA analyses for Si3N4–SPS/Ag–Cu/Cu–Zn/Nb interface shown in Fig. 9.
nitrogen or it can be released from the system as N2 gas. Prior studies
such as those performed by Maeda et al. [31] and Schuster et al. [28]
reported that Nb5Si3, NbSi2, NbN, and Nb2N intermetallic compounds
are expected to form in the Si3N4/Nb system. However, more recently,
Lemus-Ruiz et al. [3] stated that the formation of Nb5Si3 and NbN is
thermodynamically feasible above 1100 °C. Thus, niobium atoms might
diffuse through a silver-rich matrix and react with Si to form niobium
silicides (Nb5Si3) in the vicinity of the silicon nitride surface. Then,
because of their lower density, the precipitates might concentrate along
the niobium substrate surface. More recently, Ceja-Cárdenas et al. [26]
studied the formation of Nb–Si precipitates, and the authors reported
that these compounds were indirectly influenced by the sintering aids
used during sintering of the ceramic performs. A lower amount of sin-
tering aids (4 wt%) induced a greater dissociation of nitrogen and Si,
which increased the diffusion rate of Si. On the other hand, Lemus-Ruiz
et al. [32] reported that niobium silicides are brittle compounds that
cause cracks in the joining interface because of residual stresses induced
during cooling. Similar behavior was observed in the present research
work, in which cracks formed near the Si–Nb compounds (see “crack”
in Fig. 9).

Point Element (at.%) 4. Conclusions

Si Ag Cu Zn Nb Possible phase
A silicon nitride (Si3N4) ceramic was successfully joined to niobium
1 30.97 – 6.77 – 62.26 Nb5Si3 at 1000 °C for 30 min in the case of a Si3N4-CS specimen and at 1050 °C
2 32.81 – 6.36 – 60.83 Nb5Si3 for 40 min in the case of a Si3N4-SPS specimen. The following conclu-
3 32.74 0.92 4.80 – 61.54 Nb5Si3 sions were obtained based on the results of the current work:
4 – 90.85 9.15 – – Silver-rich matrix
The joining interface was characterized by copper-rich precipitates
5 0.33 3.66 95.16 – 0.85 Copper-rich
6 – – – – 100 Niobium immersed in a silver-rich matrix. Furthermore, the higher level of
porosity of the Si3N4-CS specimen permitted interaction at the metal/

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Fig. 10. EDS mapping of the elements presents in the intermetallic compounds in zone A.
ceramic interface at a lower joining temperature, in contrast to the
results obtained with the Si3N4-SPS ceramic.
The kinetic joining in the Si3N4-CS/Ag–Cu/Cu-Zn/Nb system can be
summarized as follows:
i. At 40 min, non-reactive wetting took place to promote joining,
where the silicon dissolution decreased the surface tension of the
liquid phase (derived from the filler alloys), which promoted in-
filtration into the pores of the Si3N4-CS specimen. This seemed to be
an important mechanism to permit the spreading and anchoring of
the liquid metal. However, a weak joint was observed when the
physical interaction was determined by van der Waals interaction.
ii. Reactive wetting occurred at 120 min, where an increase of the
joining temperature promoted niobium diffusion. Thus, niobium
atoms used the silver-rich matrix as a transport mechanism to react
with the ceramic surface. This improved the joint because of the
chemical reaction that took place to form an interface free of dis-
continuities
An uncontrolled reaction zone was observed near the niobium in the
Si3N4-SPS/Ag–Cu/Cu-Zn/Nb system joined at 1100 °C for 20 min,
which was composed of a Nb5Si3 binary phase with a relatively small
amount of Cu in solution.
Acknowledgments
This work is part of a bachelor thesis (MMP) and was partially
supported through projects No. DSA/103.5/15/6789 and 5801.16-P
sponsored by the Subsecretaría de Educación Superior-Programa para
el Desarrollo Profesional Docente and Tecnológico Nacional de México,
respectively. The authors wish to thank Academia de Ingeniería
Mecánica, Instituto Tecnológico de Morelia and IIMM-UMSNH for the
facilities used in this research.
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