Electromagnetic metamaterials have attracted widespread attention because of their unique properties, and the introduction of conductive metals or carbon into an insulating matrix is the main method for preparing metamaterials. Silicon nitride ceramics have become an ideal matrix for electromagnetic metamaterials because of their high degree of insulation, high thermal conductivity, high-temperature resistance, corrosion resistance, and excellent mechanical properties. However, owing to poor sintering activity, chemical incompatibility, thermal expansion mismatch, or second-phase melt agglomeration, it is difficult to prepare dense silicon nitride-based metamaterials without a mechanical pressure-assisted sintering process, which greatly limits their high-performance preparation and industrial application. To address this issue, this work proposes the use of the high melting point metal tungsten as the conductive second phase. Through the control of chemical reactions, analysis, and regulation of the densification process, the materials were fully densified by gas pressure sintering. After the introduction of tungsten, not only did the electrical and thermal conductivity properties of the silicon nitride ceramics improve, but a negative permittivity behavior was also observed when the tungsten content reached 20 vol%. A new type of dense silicon nitride-based metamaterials with great industrial potential was proposed and prepared, which can guide the preparation and industrial application of high-performance metamaterials.
Li YX, Han WB, Chen GQ, et al. The Microstructure and thermal diffusivity of carbon nanostructures/Si3N4 composites processed using spark plasma sintering. Ceram Int 2017, 43: 3435–3438.
Riley FL. Silicon nitride and related materials. J Am Ceram Soc 2000, 83: 245–265.
Tang SJ, Guo WM, Sun SK, et al. Design strategy of phase and microstructure of Si3N4 ceramics with simultaneously high hardness and toughness. J Adv Ceram 2023, 12: 122–131.
Li W, Yu ZJ, Wiehl L, et al. Hard and tough novel high-pressure γ-Si3N4/Hf3N4 ceramic nanocomposites. J Adv Ceram 2023, 12: 1418–1429.
Liu S, Liu W, Man Y, et al. Study on thermal shock resistance and attenuation law of silicon nitride ceramic materials at high temperature. Adv Ceram 2023, 44: 451–460.
Zhang W, Su L, Lu D, et al. Resilient Si3N4@SiO2 nanowire aerogels for high-temperature electromagnetic wave transparency and thermal insulation. J Adv Ceram 2023, 12: 2112–2122.
Fukuda Y, Harada K, Yonetsu M, et al. Relation between crystal structure and lattice oxygen content of sintered reaction-bonded silicon nitride. J Am Ceram Soc 2021, 104: 6563–6571.
Li JS, Yu QP, Li D, et al. Formation of hierarchical Si3N4 foams by protein-based gelcasting and chemical vapor infiltration. J Adv Ceram 2021, 10: 187–193.
Nag A, Rao RR, Panda PK. High temperature ceramic radomes (HTCR)—A review. Ceram Int 2021, 47: 20793–20806.
Wu JM, Zhang XY, Xu J, et al. Preparation of porous Si3N4 ceramics via tailoring solid loading of Si3N4 slurry and Si3N4 poly-hollow microsphere content. J Adv Ceram 2015, 4: 260–266.
Xu SS, Zhou XN, Zhi Q, et al. Anisotropic, biomorphic cellular Si3N4 ceramics with directional well-aligned nanowhisker arrays based on wood-mimetic architectures. J Adv Ceram 2022, 11: 656–664.
Chen SL, Wang L, He G, et al. Microstructure and properties of porous Si3N4 ceramics by gelcasting-self-propagating high-temperature synthesis (SHS). J Adv Ceram 2022, 11: 172–183.
Luo Y, Estevez D, Scarpa F, et al. Microwave properties of metacomposites containing carbon fibres and ferromagnetic microwires. Research 2019, 2019: 3239879.
Gholipur R, Khorshidi Z, Bahari A. Enhanced absorption performance of carbon nanostructure based metamaterials and tuning impedance matching behavior by an external AC electric field. ACS Appl Mater Inter 2017, 9: 12528–12539.
Li B, Sui G, Zhong W. Single negative metamaterials in unstructured polymer nanocomposites toward selectable and controllable negative permittivity. Adv Mater 2009, 21: 4176–4180.
Muhammad, Lim CW. From photonic crystals to seismic metamaterials: A review via phononic crystals and acoustic metamaterials. Arch Comput Method E 2022, 29: 1137–1198.
Luo WJ, Wang S, Zheng SY, et al. Dielectric response of ANb2O6 (A = Zn, Co, Mn, Ni) columbite niobates: From microwave to terahertz. J Adv Ceram 2024, 13: 1189–1197.
Wu P, Zeng YP, Wang J, et al. Realizing microwave-infrared compatible stealth via single 8YSZ coating. J Adv Ceram 2024, 13: 1535–1545.
Wood J. The top ten advances in materials science. Mater Today 2008, 11: 40–45.
Xie PT, Shi ZC, Feng M, et al. Recent advances in radio-frequency negative dielectric metamaterials by designing heterogeneous composites. Adv Compos Hybrid Mater 2022, 5: 679–695.
Cheng CB, Yan KL, Fan RH, et al. Negative permittivity behavior in the carbon/silicon nitride composites prepared by impregnation-carbonization approach. Carbon 2016, 96: 678–684.
Cheng CB, Jiang YL, Sun X, et al. Tunable negative permittivity behavior and electromagnetic shielding performance of silver/silicon nitride metacomposites. Compos Part A Appl S 2020, 130: 105753.
Cheng CB, Fan RH, Wang ZY, et al. Tunable and weakly negative permittivity in carbon/silicon nitride composites with different carbonizing temperatures. Carbon 2017, 125: 103–112.
Cheng CB, Fan RH, Wang ZY, et al. Radio-frequency negative permittivity in the graphene/silicon nitride composites prepared by spark plasma sintering. J Am Ceram Soc 2018, 101: 1598–1606.
Cheng CB, Liu YH, Shi SJ, et al. Negative permittivity behavior in carbon fibre/silicon nitride ceramic composites prepared by spark plasma sintering. Ceram Int 2021, 47: 35201–35208.
Zhang ZD, Cheng CB, Han X. Percolative cobalt/silicon nitride composites with tunable negative electromagnetic parameters. RSC Adv 2016, 6: 82478–82483.
Xu CQ, Qu YP, Fan GH, et al. Tunable and weakly negative permittivity at radio frequency range based on titanium nitride/polyethylene terephthalate composites. J Mater Sci Mater El 2018, 29: 15994–16003.
Wang LJ, Qi Q, Zheng JQ, et al. A novel thermally matched conductive phase of silicon nitride ceramics. J Phys Chem Solids 2023, 179: 111379.
Wei ZL, Liu SY, Liu DG, et al. Fabrication and properties of symmetrical W/Si3N4/W functionally graded materials by spark plasma sintering. J Alloys Compd 2022, 896: 163077.
Wang LJ, Qi Q, Zhang H, et al. The fabrication of tungsten reinforced silicon nitride ceramics by altering nitrogen pressure. Ceram Int 2019, 45: 5927–5931.
Wang LJ, Qi Q, Zhang H, et al. High tough W-added silicon nitride ceramics. Ceram Int 2019, 45: 19055–19059.
Wang LJ, Qi Q, Wang ZY, et al. The effect of tungsten introduction on the tribological properties of Si3N4 ceramics paired with GCr15 steel under nonlubricated conditions. Wear 2022, 506: 204452.
Wang LJ, Qiao ZH, Qi Q, et al. Improving abrasive wear resistance of Si3N4 ceramics with self-matching through tungsten induced tribochemical wear. Wear 2022, 494: 204254.
Hyuga H, Jones MI, Hirao K, et al. Mechanical and wear properties of Si3N4–W composites using tungsten boride powder. J Mater Res 2003, 18: 2262–2267.
Flower GL, Baskaran GS, Mohan NK, et al. The structural role of tungsten ions in PbO–Sb2O3–As2O3 glass-system by means of spectroscopic investigations. Mater Chem Phys 2006, 100: 211–216.
Rao CS, Ravikumar V, Srikumar T, et al. The role of coordination and valance states of tungsten ions on some physical properties of Li2O–Al2O3–ZrO2–SiO2 glass system. J Non-Cryst Solids 2011, 357: 3094–3102.
Kovác̆ik J. Electrical conductivity of two-phase composite material. Scripta Mater 1998, 39: 153–157.
Zhao J, Zhang XS, Ma ZN, et al. Tuning mechanical and electrical performances of B4C–TiB2 ceramics in a two-step spark plasma sintering process. J Adv Ceram 2024, 13: 518–528.
Qing YC, Wen QL, Luo F, et al. Temperature dependence of the electromagnetic properties of graphene nanosheet reinforced alumina ceramics in the X-band. J Mater Chem C 2016, 4: 4853–4862.
Liu JJ, Wang ZX, Yin B, et al. A novel method to prepare self-lubricity of Si3N4/Ag composite: Microstructure, mechanical and tribological properties. J Am Ceram Soc 2018, 101: 3745–3748.
Becher PF, Sun EY, Plucknett KP, et al. Microstructural design of silicon nitride with improved fracture toughness: I, effects of grain shape and size. J Am Ceram Soc 1998, 81: 2821–2830.