Brazing of porous Si3N4 ceramic to Invar alloy with a novel Cu–Ti filler alloy: Microstructure and mechanical properties

Porous Si₃N₄ (P–Si₃N₄) ceramic was successfully joined to Invar alloy using a Cu–Ti active brazing alloy for the first time. The interfacial reactions between the Cu–Ti filler and two dissimilar substrates were studied. The influence of brazing process on the microstructure evolution of the joint was revealed, along with the formation of an infiltration layer that permitted the bonding of P–Si₃N₄ substrate. Ti reacted with Si₃N₄ to form TiN and Ti₅Si₃ compounds, resulting in the decomposition of Si₃N₄. In addition, the reaction and diffusion dual-layer formed at the Cu–Ti/Invar interface, which was attributed to the interaction of alloy elements between the braze filler and the Invar alloy. Fe–Ti and Ni–Ti intermetallics together with Cu solid solution (s,s) constituted the microstructure of the brazing seam. In addition, the optimal shear strength of the brazed joint was 20 MPa and the fracture propagation occurred in the P–Si₃N₄ ceramic substrate adjacent to the infiltration layer during the shearing tests.     

Microstructure and mechanical properties of Si3N4/42CrMo joints brazed with TiNp modified active filler

Si₃N₄ ceramic/42CrMo steel joints were obtained by employing TiNp modified Ag–Cu–Ti active filler and subsequently the effect of TiNp content on the microstructure and mechanical properties of the joints was investigated. Microstructural examination revealed that TiN+Ti₅Si₃ reaction layer was adjacent to the Si₃N₄ ceramic while a TiC reaction layer was close to the steel substrate. With the increase of TiNp content, more fine grains and less Ag–Cu eutectic appeared in the joint and the reaction layers near the two base materials became thinner. The flexural strength of the joint obtained by four-point bending test climbed about 100% with the optimum TiNp content of 5 vol%, comparing with the case without TiNp. Thermal stress distributions in the joint were analyzed using finite element modeling computations, which accorded well with the bending test results.     

Interfacial microstructure of the Si3N4/Si3N4 joint brazed with Cu–Pd–Ti filler alloy

Si₃N₄ ceramic was jointed with itself by active brazing with a Cu–Pd–Ti filler alloy. Interfacial microstructure of the Si₃N₄/Si₃N₄ joint was analyzed by EPMA, TEM and X-ray diffract meter. The results indicate that a TiN reaction layer with a thickness about 5 μm is formed at the interface between Si₃N₄ ceramic and filler alloy. The TiN reaction layer is composed of two zones: one next to the Si₃N₄ ceramic with grains of 100 nm and the other zone that connects with the filler alloy and has grains of 1 μm. The microstructure of the joint can be described as: Si₃N₄ ceramic/TiN layer with fine grains/TiN layer with coarsen grains/Cu[Pd] solid solution. Some new phases, such as Pd₂Si, PdTiSi, Ti₅Si₃ and TiN, were formed in the Cu[Pd] solid solution interlayer. With increasing brazing temperature from 1100 °C to 1200 °C, the thickness of the TiN reaction layer is not changed. Meanwhile, the amount and size of the TiN and Pd₂Si phases in the Cu[Pd] solid solution increase, while, the amount of the PdTiSi phase decreases.     

The influence of Ti: Si3N4 ratio on the microstructure evolution of Ti–Si3N4 reaction in Cu melts

In this work, through the study of the obtained Cu–Ti–Si–N intermediate products by controlling the reaction degree of Ti and Si₃N₄ powder in Cu melts at 1250～1300 °C, the effects of different Ti: Si₃N₄ mass ratios on the microstructure evolution of Ti–Si₃N₄ reaction in Cu melts were verified. When the mass ratio of Ti: Si₃N₄ is higher, such as 3.09:1, TiN will cooperate with Ti₅Si₃ and depend on each other to nucleate and grow to form TiN/Ti₅Si₃ composites. The formed TiN are spherical and wetted by Ti₅Si₃ to uniformly disperse in Cu melts. As a result, the TiN–Ti₅Si₃ hybrid reinforced Cu matrix composites will be formed. However, when the mass ratio of Ti: Si₃N₄ is lower, such as 1.37:1, Ti and Si₃N₄ will firstly react to form TiN and Ti–Si liquid. The formed TiN are irregularly polygonal and connect with each other. The Ti–Si liquid will combine with Cu melts to form Cu–Ti–Si liquid and finally form δCu₄Si, ηCu₃Si and τ₁-CuSiTi phases during the colling stage. In this case, TiN are difficult to be wetted, and the Ti–Si₃N₄ compact will keep its original shape and not spread in Cu melts.     

Interfacial microstructure and mechanical properties of porous-Si3N4 ceramic and TiAl alloy joints vacuum brazed with AgCu filler

Porous Si₃N₄ ceramic was firstly joined to TiAl alloy using an AgCu filler alloy. The effects of brazing temperature and holding time on the interfacial microstructure and mechanical properties of porous-Si₃N₄/AgCu/TiAl joints were studied. The typical interfacial microstructure of joints brazed at 880 °C for 15 min was TiAl/AlCu₂Ti/Ag-Cu eutectic/penetration layer (Ti₅Si₃+TiN, Si₃N₄, Ag (s, s), Cu (s, s))/porous-Si₃N₄. The penetration layer was formed firstly in the brazing process. With increasing brazing temperature and time, the thickness of the penetration layer increased. A large amount of element Ti was consumed in the penetration layer which suppressed the formation and growth of other intermetallic compounds. The penetration layer led the fracture to propagate in the porous Si₃N₄ ceramic substrate. The maximum shear strength was ~13.56 MPa.     

Microstructure and mechanical properties of the Si3N4/42CrMo steel joints brazed with Ag–Cu–Ti + Mo composite filler

The Si₃N₄ ceramic was joined to 42CrMo steel using Ag–Cu–Ti + Mo composite filler. Effect of Mo particles content on the microstructure and mechanical properties of the joints were investigated. Defect-free joints were received when the Si₃N₄/42CrMo steel joints were brazed with Ag–Cu–Ti + Mo composite filler. The results show that a continuous reaction layer which is composed of TiN and Ti₅Si₃ was formed near the Si₃N₄ ceramic. A double reaction layer which consists of Fe₂Ti and FeTi was also formed adjacent to 42CrMo steel, with Fe₂Ti being located near the steel. The central part of the joint is composed of Ag based solid solution, Cu based solid solution, Mo particles and some Cu–Ti intermetallic compounds. The maximal bending strength reached 587.3 MPa with 10 vol.% Mo particles in the joint, at which the joint strength was 414.3% higher than the average strength for the case without Mo particles addition.     

Microstructure evolution of Si3N4/Si3N4 joint brazed with Ag–Cu–Ti + SiCp composite filler

The Si₃N₄ ceramic was brazed by Ag–Cu–Ti + SiCp composite filler (p = particle) prepared by mechanical mixing. Effects of the content of Ti and SiC particles on microstructure of the joint were investigated. A reliable Si₃N₄/Si₃N₄ joint was achieved by using Ag–Cu–Ti + SiCp composite filler at 1173 K for 10 min. A continuous and compact reaction layer, with a suitable thickness, forms at the Si₃N₄/braze interface. The SiC particles react with Ti in the brazing layers, forming Ti₃SiC₂ thin layers around the SiC particles themselves and Ti₅Si₃ small particles in the Ag[Cu] and Cu[Ag] based solid solution. The higher content of SiC particles in the filler (≥10 vol%) depresses interfacial bonding strength between the Si₃N₄ substrate and composite brazing layer due to the thinner reaction layer and the bad fluidity of the filler. The Ti₃SiC₂ → TiC + Ti₅Si₃ reaction occurs when Ti concentration around SiC particles in the filler increases.     

Wetting of AgCu-Ti filler on porous Si3N4 ceramic and brazing of the ceramic to TiAl alloy

The effect of Ti content on the wettability of AgCu-Ti filler on porous Si₃N₄ ceramic was studied by the sessile drop method. AgCu-2 wt% Ti filler alloy showed a minimum contact angle of 14.6° on porous Si₃N₄ ceramic during the isothermal wetting process. The mechanism of AgCu-Ti filler wetting on porous Si₃N₄ ceramic is clarified in this paper. Porous Si₃N₄ ceramic was brazed to TiAl alloy using AgCu-xTi (x = 0, 2 wt%, 4 wt%, 6 wt%, 8 wt%) filler alloy at 880 °C for 10 min. The effect of Ti content on the interfacial microstructure and mechanical properties of porous-Si₃N₄/AgCu-xTi/TiAl joints are studied. The typical interfacial microstructure of p-Si₃N₄/AgCu-Ti/TiAl joint is p-Si₃N₄/penetration layer (Ag(s,s)+Si₃N₄+TiN+Ti₅Si₃)/Ag(s,s)+Cu(s,s)+TiCu/AlCu₂Ti/TiAl. The maximum shearing strength of the brazed joint was 14.17 MPa and fracture that occurred during the shearing test propagated in the porous Si₃N₄ ceramic substrate for the formation of the penetration layer.     

Microstructure and reaction phases in Si3N4/Si3N4 joint brazed with Cu–Pd–Ti filler alloy

Si₃N₄ ceramic was self-jointed using a filler alloy of Cu–Pd–Ti, and the microstructure of the joint was analyzed. By using a filler alloy of Cu76.5Pd8.5Ti15 (at.%), a high quality Si₃N₄/Si₃N₄ joint was obtained by brazing at 1100–1200 °C for 30 min under a pressure of 2 × 10⁻³ MPa. The microstructure of the Si₃N₄/Si₃N₄ joint which was observed by EPMA, XRD and TEM, and the results indicated that a reaction layer of TiN existed at the interface between Si₃N₄ ceramic and filler alloy. The center of the joint was Cu base solid solution containing Pd, and some reaction phases of TiN, PdTiSi and Pd₂Si found in the Cu [Pd] solid solution.     

Interfacial microstructure and mechanical properties of TC4/Ti3SiC2 contact-reactive brazed joints using a Cu interlayer

Reliable contact-reactive brazed joints of TC4 alloy and Ti₃SiC₂ ceramic were obtained using a Cu interlayer. The interfacial microstructure of a TC4/Ti₃SiC₂ joint brazed at 920?°C for 10?min was TC4/Ti₂Cu +?α-Ti +?β-Ti/Ti₂Cu +?AlCu₂Ti +?Ti₅Si₃/Ti₅Si₃ +?Ti₅Si₄/Ti₃SiC₂. The interfacial microstructure and mechanical properties of TC4/Ti₃SiC₂ joints brazed at different temperatures were investigated. With increasing temperature, the shear strength of the brazed joints first increased and then decreased. The maximum shear strength was 132?±?8?MPa, and the corresponding fracture occurred along the Ti–Si reaction layer and the Ti₃SiC₂ substrate adjacent to the Ti–Si reaction layer. The microhardness test also demonstrated that the Ti–Si reaction layer possessed the highest microhardness, 812?±?22 HV. The Ti-Si reaction layer was the weakest part of the brazed joints. To eliminate the Ti-Si reaction layer and improve the mechanical properties of TC4/Ti₃SiC₂ brazed joints, a 40-μm Ni layer was plated on the surface of the Ti₃SiC₂ ceramic before brazing. The results showed that the Ti–Si reaction layer that formed adjacent to the Ti₃SiC₂ ceramic was thin and intermittent. Moreover, the interface between the Ti₃SiC₂ ceramic and the TC4 alloy became jagged. The shear strength of the TC4/nickel-plated Ti₃SiC₂ brazed joints improved to 148?±?8?MPa; the corresponding fracture occurred mainly in the Ti₃SiC₂ ceramic and only a small portion of the fracture occurred in the brazing seam.     

Linking microstructure evolution and impedance behaviors in spark plasma sintered Si3N4/TiC and Si3N4/TiN ceramic nanocomposites

We proposed a novel approach to investigate the three-dimensional microstructures and sintering behaviors of Si₃N₄-based ceramic nanocomposites by electrochemical impedance spectroscopy. Si₃N₄/TiC and Si₃N₄/TiN with various weight percentages of conductive phases were prepared by spark plasma sintering (SPS) at different temperatures and dwell times. The incorporation of TiC and TiN into β-Si₃N₄ provides pulse current paths inside the ceramics due to their higher conductivity. These paths enable the localized Joule heating and mass transport, facilitating the densification and grain growth of ceramic compact. The electrochemical study of such nanocomposites has revealed three-dimensional information of the evolution of their microstructures, and the capacitive and resistive characteristics of the nanocomposites reflect the densification, grain growth, and element distribution in the compact. The impedance model presented in this work suggests isolated distribution of TiN in Si₃N₄ while Si₃N₄/TiC of the same amount of additives at the same sintering conditions formed conductive network. This impedance analysis further explained the differences in densification mechanism of SPS in Si₃N₄/TiN and Si₃N₄/TiC.     

Identification and quantification of reaction phases at Si3N4–Ti interfaces by using analytical transmission electron microscopy techniques

Silicon nitride (Si₃N₄) and titanium (Ti) were successfully bonded by using a capacitor discharge joining method. The resulting sample interfaces were characterized by scanning electron microscopy (SEM) and analytical transmission electron microscopy (TEM) techniques. SEM and chemical analyses by energy dispersive X-ray spectrometry (EDX) and wave length X-ray spectrometry (WDX) showed that if there is a reaction layer it is very small. Sample preparation from metal–ceramic joints for TEM by using conventional techniques is difficult. To overcome this problem, samples were prepared by using a focus ion beam (FIB) and investigated by TEM techniques. Analytical TEM techniques such as electron energy loss spectroscopy (EELS) revealed that Si₃N₄ interacted with Ti and reaction phases were formed at the interface. These phases are approximately 50 nm thick Ti₃N₂ layer at the interface next to Si₃N₄ followed by continuous Ti₆Si₃N phase as a matrix containing Ti₃N particles.     

Interfacial microstructure and mechanical properties of Ti3SiC2 ceramic and TC11 alloy joint diffusion bonded with a Cu interlayer

Reliable joints of Ti₃SiC₂ ceramic and TC11 alloy were diffusion bonded with a 50 μm thick Cu interlayer. The typical interfacial structure of the diffusion boned joint, which was dependent on the interdiffusion and chemical reactions between Al, Si and Ti atoms from the base materials and Cu interlayer, was TC11/α-Ti + β-Ti + Ti₂Cu + TiCu/Ti₅Si₄ + TiSiCu/Cu(s, s)/Ti₃SiC₂. The influence of bonding temperature and time on the interfacial structure and mechanical properties of Ti₃SiC₂/Cu/TC11 joint was analyzed. With the increase of bonding temperature and time, the joint shear strength was gradually increased due to enhanced atomic diffusion. However, the thickness of Ti₅Si₄ and TiSiCu layers with high microhardness increased for a long holding time, resulting in the reduction of bonding strength. The maximum shear strength of 251 ± 6 MPa was obtained for the joint diffusion bonded at 850 °C for 60 min, and fracture primarily occurred at the diffusion layer adjacent to the Ti₃SiC₂ substrate. This work provided an economical and convenient solution for broadening the engineering application of Ti₃SiC₂ ceramic.     

Copper bonding silicon nitride substrate using atmosphere plasma spray

Silicon nitride (Si₃N₄) is an excellent engineering ceramic with high strength, fracture toughness, wear resistance, and good chemical and thermal stability. Recently, the enhanced thermal conductivity enables Si₃N₄ to have potential application prospects in the electronic and orthopedic fields. Metal bonding with Si₃N₄ is often the key to these applications. Here we report a facile approach for the titanium-activated Cu bonding on Si₃N₄ substrates using an atmosphere plasma spray (APS) process. With X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) observation, it was shown that the interaction between the pre-bonded Ti (by APS) on Si₃N₄ promoted the adhesion and high bonding strength of APS Cu on Si₃N₄. The interfacial structure and phases were characterized, and tensile strength, electrical resistivity, thermal conductivity, and residual stress of Cu bonded Si₃N₄ were measured accordingly. The APS deposited Cu layer is dense, has a high purity, and is joined firmly with Ti pre-bonded Si₃N₄ substrate. The maximum tensile strength between Cu and Si₃N₄ is as high as 89.4 MPa. The Si₃N₄ substrate bonded with highly dense Cu demonstrates a low surface resistivity of 8.72 × 10⁻⁴ Ω∙mm, and high thermal conductivity of 98.12 W/m·K, which shows potential applications in electronic devices.     

Graphene nanoplatelets reinforced AgCuTi composite filler for brazing SiC ceramic

Graphene nanoplatelets (GNPs) were used as reinforcement in AgCuTi filler for brazing SiC ceramic. Ti from the filler reacted with SiC ceramic to form TiC and Ti₅Si₃ adjacent to the SiC ceramic. According to the TEM and HRTEM results, TiC layer exhibited good lattice matching with SiC substrate. TiC particles synthesized by the reaction between Ti and GNPs in situ promoted the heterogeneous nucleation of TiCu and Cu(s,s), and contributed to the refinement of microstructure. Shear tests results indicated that the adoption of GNPs affected the joint property significantly. The TiC particles and an appropriate TiC + Ti₅Si₃ layer thickness both relieved the residual stress of the brazed joint and thereby increased the joint strength. The shear strength of the joint reached the maximum value of 38 MPa when using AgCuTi/GNPs (GNPs reinforced AgCuTi) composite filler containing 1% GNPs, which was ～139% higher than that of the joint brazed with AgCuTi filler.     

Effect of high temperature cycling on both crack formation in ceramics and delamination of copper layers in silicon nitride active metal brazing substrates

Crack formation in Si₃N₄ active metal brazing (AMB) ceramic substrates and delamination of copper layers on the AMB substrates subjected to temperature cycling from −40 to 250 °C were investigated to evaluate the reliability of these substrates under harsh environments. Acoustic scanning microscopy (ASM) observation of the Si₃N₄ substrates with 0.30 mm thick Cu layers revealed crack formation beneath the corner of the copper plate after 100 cycles, whereas no cracks were detected on the Si₃N₄ substrate with a 0.15 mm thick Cu layer, even after 1000 cycles. The residual bending strength of the Si₃N₄ substrates with 0.30 mm thick Cu layers was 78% of the as-received substrate after 10 thermal cycles, and gradually decreased with an increase in the number of thermal cycles until ca. 65% of the initial strength after 1000 cycles. The Si₃N₄ substrates with 0.15 mm thick Cu layers exhibited a gentler degradation of residual strength than those with 0.30 mm thick Cu layers. In contrast, the residual bending strength of AlN-AMB substrates with 0.15 mm or 0.30 mm thick Cu layers were reduced by 50% within only 10 thermal cycles. The depth of cracks developed during the thermal cycles was measured from the fractured surface of the Si₃N₄-AMB and AlN-AMB substrates. The crack-growth rate in the Si₃N₄-AMB substrates was much slower than that in the AlN-AMB substrates, which could account for the different degradation behavior of the residual bending strength.     

MPCVD diamond coating of Si3N4–TiN electroconductive composite substrates

A study of microwave plasma (MPCVD) diamond deposition on Si₃N₄–TiN composites with different TiN amounts (0–30 vol.% TiN) is performed. These ceramic composites are requested in order to obtain a suitable material to be cut by electrodischarge machining (EDM), aiming their use as substrates for cutting tools and tribological components. TiN is an electrical conductor, contrarily to Si₃N₄, but it is characterized by a higher thermal expansion coefficient value than Si₃N₄ and diamond. The estimated thermal stresses are found to be low and tensile (0.90 GPa) when using the monolithic Si₃N₄ substrate, but compressive for the Si₃N₄–TiN composites, and even relatively high in magnitude (− 1.9 GPa) for the Si₃N₄–30 vol.% TiN composite. Brale indentation assessed the adhesion strength of diamond on the different substrate grades. Optimal behaviour (very low residual stress; no film delamination under 1000 N) is observed for the Si₃N₄–9 vol.% TiN substrate, corresponding to the lowest thermal mismatch and minimal residual stress magnitude.     

Diffusion bonding of silicon nitride to titanium

Abstract

Si₃ N₄ /Ti and Si₃ N₄ /Ti/Si₃ N₄ combinations were joined by solid state diffusion bonding using hot pressing at temperatures ranging from 1200 to 1500°C. The microstructure of the resulting interfaces was characterised by scanning electron microscopy, electron probe microanalysis, and XRD. Si₃ N₄ /Ti samples hot pressed at temperatures less than 1400°C could not be bonded. However, at 1400°C bonding of single joints occurred, although the samples debonded during SEM preparation. Hot pressing at 1500°C resulted in effective joining by the formation of a reactive interface. For Si₃ N₄ /Ti/Si₃ N₄ sandwich samples hot pressed at 1400 and 1500°C, successful joining of Si₃ N₄ to Ti occurred by the formation of an interface on the Ti side. The surface roughness of the joint materials plays an important role, affecting the thickness of the reaction products. The interfaces grew in a parabolic fashion with the formation of various titanium silicides (Ti₅ Si₃ and TiSi) as well as titanium nitride (TiN).     

Microstructure and mechanical properties of porous Si3N4/Invar joints brazed with Ag-Cu-Ti+Mo/Cu/Ag-Cu multi-layered composite filler

Ag-Cu-Ti/Cu/Ag-Cu multi-layered filler was successfully designed to braze porous Si₃N₄ and Invar alloy. To further reduce the CTE mismatch between the porous Si₃N₄ and brazing filler, Mo particles were introduced into Ag-Cu-Ti. The effects of the Mo addition on the microstructure and mechanical properties of the brazed joints were studied. The results showed that, the addition of Mo particles into Ag-Cu-Ti lowered the CTE mismatch and improved the joint strength to a certain degree. However, an excessive content was harmful. The Mo particles could absorb Ti at high temperature, causing Ti shortage in the reaction with the ceramic. When cooling down, the absorbed Ti was released. The released Ti could react with Cu to generate Cu-Ti phase. So, additional Ti was adopted in the brazing filler as a supplement. When the Ti content was 5 wt%, the reaction layer on the ceramic interface was too thin to transfer enough load. However, when it reached 15 wt%, the Cu interlayer dissolved completely and Fe-Ti and Ni-Ti phases appeared. The maximum joint shear strength (83 MPa) was obtained with 10 wt% Ti and 5 vol% Mo, which had exceeded 90% of the porous Si₃N₄ and was 56% higher than the joint brazed without Mo particles.     

Interfacial microstructure and strengthening mechanism of BN-doped metal brazed Ti/SiO2-BN joints

Ag–Cu–Ti + BN composite filler was developed to braze SiO₂-BN ceramic and titanium. The effects of BN particles content on the microstructure and mechanical properties of the joints were investigated. The fine TiB whiskers and TiN particles were synthesized in the brazing seam by introducing BN particles. TiN–TiB₂ reaction layer formed adjacent to SiO₂-BN ceramic while Ti–Cu compound layer formed at Ti substrate. With the increase of BN content, more fine-grains formed in the joint and the reaction layer nearby the base materials became thinner. The hardness and modulus of the reaction phases were characterized by nanoindentations to reveal the plastic deformability of the brazing seam. The improvement of the joint strength was 340% with 3 wt.% BN addition. The joint strength was determined by the thermal expansion mismatch between the joined materials, plastic deformation in the brazing seam, and interfacial structure of the joint.