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Materials Characterization
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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 filler alloy at temperatures from 840 to 900 °C using different holding
times. The authors observed cracks in the joining interface. They
Silicon nitride (Si3N4) ceramics possess high hardness, low density, therefore concluded that the mismatch in the coefficients of thermal
good corrosion resistance, thermal stability and resistance to thermal expansion between the base materials and the precipitation of brittle
shock. These materials are used for high-temperature and corrosive intermetallic compounds at the bond line led to residual stress forma-
environments such as in turbochargers and auxiliary power unit com- tion on the joining interface. One way to overcome this problem is to
ponents for aircraft as reported by Singh et al. [1]. However, it is dif- use multiple interlayers with different thermal expansion coefficients,
ficult to produce complex ceramic shapes with complete densification. as reported by Blugan et al. [5]. According to Zhang et al. [6], elements
Thus, joining simple ceramic pieces with complex metal components such as Cu and Zn have been used as soft ductile interlayers to absorb
has become a key technology to overcoming such problems in manu- the residual stresses caused by the thermal expansion mismatch. More
facturing. Brazing is among the techniques used to join ceramics to recently, Fernie et al. [7] suggested that a Ag–Cu eutectic alloy is re-
metals to produce complex components for structural applications, and latively ductile and therefore able to produce crack-free joints. The
it is receiving extensive attention because of its simplicity and cost- second issue is the poor wettability of ceramics by non-reactive brazing
effectiveness [2]. Brazing is a joining process where a filler metal with a filler metals. Do Nascimiento et al. [8] reported that the wetting process
low melting point is heated to form a liquid phase, which is then dis- can be either physical or chemical, depending on the nature of the
tributed between the base materials to be joined. However, there are bonding between the solid and liquid. Physical (non-reactive) wetting
two essential issues that remain unsolved. The first is the thermal ex- occurs when reversible van der Waals forces act at the interface. León-
pansion mismatch between the ceramic and the metal, which induces Patiño et al. [9] joined a Cu–Al2O3 composite to a Cu substrate using
residual stresses during cooling, causing cracks in the joining interface, Cu–Zn and Ag–Cu alloys as filler metals. The authors stated that for-
as observed by Lemus-Ruiz et al. [3]. Xu and Indacochea [4] studied the mation of the joint was promoted by non-reactive wetting in which the
effect of temperature on Si3N4/410-SS assemblies using a Ag–Cu–Ti 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
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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M. Morales-Pérez, L. Ceja-Cárdenas Materials Characterization 131 (2017) 316–323
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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M. Morales-Pérez, L. Ceja-Cárdenas Materials Characterization 131 (2017) 316–323
Fig. 5. EDS mapping of the elements present in the Si3N4-CS/Ag-Cu/Cu–Zn/Nb interface joined at 1000 °C/120 min.
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M. Morales-Pérez, L. Ceja-Cárdenas Materials Characterization 131 (2017) 316–323
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.
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