Reliable brazing joints of Al2O3 ceramics were obtained using an active Ni‒Ti interlayer under vacuum conditions. The interfacial microstructure and mechanical properties of the joints were studied. The structural, electronic, and elastic properties of the primary interfacial reaction phases were determined using first–principles calculations. After brazing at 1320 °C for 30 min, Ni2Ti4O layer and columnar AlNi2Ti formed at the interface adjacent to the Al2O3 substrate. With increasing brazing temperature between 1300 °C and 1380 °C, Ni2Ti4O layer thickened gradually, and the AlNi2Ti became increasingly longer. As brazing temperature reached 1400 °C, TiO was formed at the interface, and the Ni2Ti4O content decreased significantly; moreover, bulk AlNi2Ti and TiNi3 were distributed in the brazing seam. The highest shear strength of 129 MPa was achieved when brazed at 1350 °C for 30 min. According to the first–principles calculations, Ni2Ti4O is more readily formed than AlNi2Ti, whereas AlNi2Ti exhibits greater stability than Ni2Ti4O. Both AlNi2Ti and Ni2Ti4O possess metallic bonds, contributing to the adhesion of the filler metal to the Al2O3 substrates. The calculated modulus and Poisson’s ratio indicate that both AlNi2Ti and Ni2Ti4O exhibit ductile characteristics, which assist in relieving residual stress within the joint.
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