Additive Manufacturing of Cupric Oxide via Direct Ink Writing

Muhammad Ali; Shaheryar A. Khan; Aqueel Shah; Antash Najib; Abbas Hussain

doi:10.36561/ING.30.3

Authors

Muhammad Ali National University of Sciences and Technology, Pakistán https://orcid.org/0009-0006-8014-5737
Shaheryar A. Khan DHA Suffa University, Pakistán https://orcid.org/0000-0003-1600-7322
Aqueel Shah University of Sciences and Technology, Pakistán
Antash Najib National University of Sciences and Technology, Pakistán https://orcid.org/0000-0002-4845-9350
Abbas Hussain National University of Sciences and Technology, Pakistán https://orcid.org/0009-0008-1680-6507

DOI:

https://doi.org/10.36561/ING.30.3

Keywords:

Advanced Ceramics, Direct Ink Writing, Additive Manufacturing, Copper Oxide, Cupric Oxide, Binder, Ceramics, Green Body, Brown Body, Sintered Ceramic, Resistivity Analysis of Ceramic, Aqueous Binder Slurry, Particle Laden Slurry

Abstract

The DIW approach offers numerous benefits, including expedited prototyping, cost-effectiveness, reduced waste in manufacturing, and enhanced design flexibility. It's currently a popular production method for building materials and has great potential for porous and electronic materials. In this study, porous cupric oxide (CuO) ceramics were fabricated using a direct ink writing (DIW) approach based on a copper particle–laden aqueous precursor. The ink formulation was optimized to achieve stable extrusion and crack-free green bodies, yielding a final composition of 68.0 wt% Cu, 31.3 wt% water, and 0.6 wt% CMC. Following oxidation and sintering in air, the printed structures exhibited a bulk density of 3.60 ± 0.20 g cm⁻³ and a corresponding theoretical porosity of 43.7 ± 0.9%. X-ray diffraction confirmed nearly phase-pure monoclinic CuO with no detectable Cu or Cu₂O residues. The printed components exhibited an interconnected, porous microstructure and a four-point-probe resistivity of 10.5 ± 0.3 Ω·m at 25 °C, reflecting the influence of high porosity on charge transport. The DIW route demonstrated here provides a controllable pathway for producing porous CuO architectures with tunable microstructure and moderate electrical conductivity. These characteristics suggest potential applicability in gas filtration, catalytic supports, and electrochemical sensing; however, device-level validation is still required to fully assess functional performance.

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References

W.R. Matizamhuka, Advanced ceramics — The new frontier in modern-day technology: Part I, J South Afr Inst Min Metall 118 (2018) 757–764. https://doi.org/10.17159/2411-9717/2018/V118N7A9.

T. Ayode Otitoju, P. Ugochukwu Okoye, G. Chen, Y. Li, M. Onyeka Okoye, S. Li, Advanced ceramic components: Materials, fabrication, and applications, Journal of Industrial and Engineering Chemistry 85 (2020) 34–65. https://doi.org/10.1016/J.JIEC.2020.02.002.

C.Barry. Carter, M.Grant. Norton, Ceramic materials: science and engineering, (2013). https://books.google.com/books/about/Ceramic_Materials.html?id=WRg_AAAAQBAJ (accessed March 26, 2023).

R. Danzer, On the relationship between ceramic strength and the requirements for mechanical design, J Eur Ceram Soc 34 (2014) 3435–3460. https://doi.org/10.1016/J.JEURCERAMSOC.2014.04.026.

F. Klocke, Modern approaches for the production of ceramic components, J Eur Ceram Soc 17 (1997) 457–465. https://doi.org/10.1016/S0955-2219(96)00163-X.

H. Budharaju, S. Suresh, M.P. Sekar, B. De Vega, S. Sethuraman, D. Sundaramurthi, D.M. Kalaskar, Ceramic materials for 3D printing of biomimetic bone scaffolds – Current state-of-the-art & future perspectives, Mater Des 231 (2023) 112064. https://doi.org/10.1016/J.MATDES.2023.112064.

M. Laborie, A. Naveau, A. Menard, CAD-CAM resin-ceramic material wear: A systematic review, J Prosthet Dent (2022). https://doi.org/10.1016/J.PROSDENT.2022.01.027.

Susilawati, T.I. Nasution, M. Hasanah, Y.A. Sihombing, Fabrication of Ceramic Composites Based on CuO-ZnO, (2018). https://dupakdosen.usu.ac.id/handle/123456789/69927 (accessed April 1, 2023).

D. Renuga, J. Jeyasundari, S. Athithan, Y. Brightson, A. Jacob, Synthesis and characterization of copper oxide nanoparticles using Brassica oleracea var. italic extract for its antifungal application, Mater. Res. Express 7 (2020) 45007. https://doi.org/10.1088/2053-1591/ab7b94.

S. Steinhauer, E. Brunet, T. Maier, G.C. Mutinati, A. Köck, O. Freudenberg, C. Gspan, W. Grogger, A. Neuhold, R. Resel, Gas sensing properties of novel CuO nanowire devices, Sens Actuators B Chem 187 (2013) 50–57. https://doi.org/10.1016/J.SNB.2012.09.034.

D.G. Desai, G.R. Navale, D.J. Late, M.S. Dharne, P.S. Walke, Size does matter: antibacterial activities and cytotoxic evaluation of polymorphic CuO nanostructures, J Mater Sci 58 (2023) 2782–2800. https://doi.org/10.1007/S10853-023-08157-4/METRICS.

A.P. Cabello, M.A. Ulla, J.M. Zamaro, In situ growth of nanostructured copper and zinc mixed oxides on brass supports as efficient microreactors for the catalytic CO oxidation, Journal of Materials Science 2022 57:27 57 (2022) 12797–12809. https://doi.org/10.1007/S10853-022-07391-6.

B.K. Singh, State-of-Art on Self-Lubricating Ceramics and Application of Cu/CuO as Solid Lubricant Material, Https://Doi.Org/10.1080/0371750X.2022.2149625 (2023). https://doi.org/10.1080/0371750X.2022.2149625.

L.E. Román, C. Villalva, C. Uribe, F. Paraguay-Delgado, J. Sousa, J. Vigo, C.M. Vera, M.M. Gómez, J.L. Solís, Textiles Functionalized with Copper Oxides: A Sustainable Option for Prevention of COVID-19, Polymers 2022, Vol. 14, Page 3066 14 (2022) 3066. https://doi.org/10.3390/POLYM14153066.

A.M. Anand, A. Raj, R. Adithya Nath, J.A. Salam, R. Jayakrishnan, Self-powered UV photodetector based on self-assembled CuO and spin-coated ZnO heterostructure, J Mater Sci 58 (2023) 11000–11015. https://doi.org/10.1007/S10853-023-08726-7/METRICS.

R. Ahmad, M. Vaseem, N. Tripathy, Y.B. Hahn, Wide linear-range detecting nonenzymatic glucose biosensor based on CuO nanoparticles inkjet-printed on electrodes, Anal Chem 85 (2013) 10448–10454. https://doi.org/10.1021/AC402925R.

K. Abdelkarem, R. Saad, A.M. Ahmed, M.I. Fathy, M. Shaban, H. Hamdy, Efficient room temperature carbon dioxide gas sensor based on barium doped CuO thin films, J Mater Sci 58 (2023) 11568–11584. https://doi.org/10.1007/S10853-023-08687-X/TABLES/3.

D.Y. Tiba, L.L. Name, R. Landers, T.C. Canevari, Copper oxide nanostructures with nanoneedles shape obtained by direct reaction with nitrogen-doped carbon quantum dots: development of an electrochemical sensor to glyphosate, J Mater Sci 58 (2023) 12569–12583. https://doi.org/10.1007/S10853-023-08827-3/METRICS.

U.A.A. Yasin, M.M. Ahmed, J. Zhang, Z. Jia, T. Guo, R. Zhao, J. Shi, J. Du, Engineering the band structure of CuO via decoration with AgBr to enhance its photocatalytic degradation performance, J Mater Sci 58 (2023) 7333–7346. https://doi.org/10.1007/S10853-023-08487-3/METRICS.

N. Bin Tanvir, C. Wilbertz, S. Steinhauer, A. Köck, G. Urban, O. Yurchenko, Work Function Based CO2 Gas Sensing Using Metal Oxide Nanoparticles at Room Temperature, Mater Today Proc 2 (2015) 4190–4195. https://doi.org/10.1016/J.MATPR.2015.09.002.

O. Baranov, K. Bazaka, T. Belmonte, C. Riccardi, H.E. Roman, M. Mohandas, S. Xu, U. Cvelbar, I. Levchenko, Recent innovations in the technology and applications of low-dimensional CuO nanostructures for sensing, energy and catalysis, Nanoscale Horiz (2023). https://doi.org/10.1039/D2NH00546H.

O. Lupan, V. Postica, N. Ababii, M. Hoppe, V. Cretu, I. Tiginyanu, V. Sontea, T. Pauporté, B. Viana, R. Adelung, Influence of CuO nanostructures morphology on hydrogen gas sensing performances, Microelectron Eng 164 (2016) 63–70. https://doi.org/10.1016/J.MEE.2016.07.008.

F. Shao, F. Hernández-Ramírez, J.D. Prades, C. Fàbrega, T. Andreu, J.R. Morante, Copper (II) oxide nanowires for p-type conductometric NH 3 sensing, Appl Surf Sci 311 (2014) 177–181. https://doi.org/10.1016/J.APSUSC.2014.05.038.

S. Wang, S. Gao, J. Tian, Q. Wang, T. Wang, X. Hao, F. Cui, A stable and easily prepared copper oxide catalyst for degradation of organic pollutants by peroxymonosulfate activation, J Hazard Mater 387 (2020) 121995. https://doi.org/10.1016/J.JHAZMAT.2019.121995.

T.H. Tran, V.T. Nguyen, Review Article Copper Oxide Nanomaterials Prepared by Solution Methods, Some Properties, and Potential Applications: A Brief Review, (2014). https://doi.org/10.1155/2014/856592.

J.O. Ighalo, P.A. Sagboye, G. Umenweke, O.J. Ajala, F.O. Omoarukhe, C.A. Adeyanju, S. Ogunniyi, A.G. Adeniyi, CuO nanoparticles (CuO NPs) for water treatment: A review of recent advances, Environ Nanotechnol Monit Manag 15 (2021). https://doi.org/10.1016/J.ENMM.2021.100443.

S. Saif, S.F. Adil, M. Khan, M.R. Hatshan, M. Khan, F. Bashir, Adsorption Studies of Arsenic(V) by CuO Nanoparticles Synthesized by Phyllanthus emblica Leaf-Extract-Fueled Solution Combustion Synthesis, Sustainability 2021, Vol. 13, Page 2017 13 (2021) 2017. https://doi.org/10.3390/SU13042017.

L. Mohammadi, E. Bazrafshan, M. Noroozifar, A. Ansari-Moghaddam, F. Barahuie, D. Balarak, Adsorptive Removal of Benzene and Toluene from Aqueous Environments by Cupric Oxide Nanoparticles: Kinetics and Isotherm Studies, J Chem 2017 (2017). https://doi.org/10.1155/2017/2069519.

Z. Liu, C. Ma, Z. Chang, P. Yan, F. Li, Advances in crack formation mechanism and inhibition strategy for ceramic additive manufacturing, J Eur Ceram Soc 43 (2023) 5078–5098. https://doi.org/10.1016/J.JEURCERAMSOC.2023.05.008.

S.S. Hossain, K. Lu, Recent progress of alumina ceramics by direct ink writing: Ink design, printing and post-processing, Ceram Int 49 (2023) 10199–10212. https://doi.org/10.1016/J.CERAMINT.2023.01.143.

J. xin Wen, T. bin Zhu, Z. peng Xie, W. bin Cao, W. Liu, A strategy to obtain a high-density and high-strength zirconia ceramic via ceramic injection molding by the modification of oleic acid, International Journal of Minerals, Metallurgy and Materials 24 (2017) 718–725. https://doi.org/10.1007/S12613-017-1455-9/METRICS.

S.M. Olhero, P.M.C. Torres, J. Mesquita-Guimarães, J. Baltazar, J. Pinho-da-Cruz, S. Gouveia, Conventional versus additive manufacturing in the structural performance of dense alumina-zirconia ceramics: 20 years of research, challenges and future perspectives, J Manuf Process 77 (2022) 838–879. https://doi.org/10.1016/J.JMAPRO.2022.02.041.

A. Vevers, A. Kromanis, E. Gerins, J. Ozolins, Additive Manufacturing and Casting Technology Comparison: Mechanical Properties, Productivity and Cost Benchmark, Latvian Journal of Physics and Technical Sciences 55 (2018) 56–63. https://doi.org/10.2478/LPTS-2018-0013.

Y. Lin, D. Wang, C. Yang, W. Zhang, Z. Wang, An Al-Al interpenetrating-phase composite by 3D printing and hot extrusion, International Journal of Minerals, Metallurgy and Materials 30 (2023) 678–688. https://doi.org/10.1007/S12613-022-2543-Z/METRICS.

Y. tao Gao, T. hua Wu, Y. Zhou, Application and prospective of 3D printing in rock mechanics: A review, International Journal of Minerals, Metallurgy and Materials 28 (2021) 1–17. https://doi.org/10.1007/S12613-020-2119-8/METRICS.

A. Zocca, P. Colombo, C.M. Gomes, J. Günster, Additive Manufacturing of Ceramics: Issues, Potentialities, and Opportunities, Journal of the American Ceramic Society 98 (2015) 1983–2001. https://doi.org/10.1111/JACE.13700.

R. Galante, C.G. Figueiredo-Pina, A.P. Serro, Additive manufacturing of ceramics for dental applications: A review, Dental Materials 35 (2019) 825–846. https://doi.org/10.1016/J.DENTAL.2019.02.026.

B. Diepold, N. Vorlaufer, S. Neumeier, T. Gartner, M. Göken, Optimization of the heat treatment of additively manufactured Ni-base superalloy IN718, International Journal of Minerals, Metallurgy and Materials 27 (2020) 640–648. https://doi.org/10.1007/S12613-020-1991-6/METRICS.

S. Ford, M. Despeisse, Additive manufacturing and sustainability: an exploratory study of the advantages and challenges, J Clean Prod 137 (2016) 1573–1587. https://doi.org/10.1016/J.JCLEPRO.2016.04.150.

M. Srivastava, S. Rathee, V. Patel, A. Kumar, P.G. Koppad, A review of various materials for additive manufacturing: Recent trends and processing issues, (2022). https://doi.org/10.1016/j.jmrt.2022.10.015.

H. Liu, J. Wu, S. Wang, J. Duan, H. Shao, Effect of Sr2+ on 3D gel-printed Sr3−xMgx(PO4)2 composite scaffolds for bone tissue engineering, International Journal of Minerals, Metallurgy and Materials 30 (2023) 2236–2244. https://doi.org/10.1007/S12613-023-2638-1/METRICS.

M.A.S.R. Saadi, A. Maguire, N.T. Pottackal, M.S.H. Thakur, M.M. Ikram, A.J. Hart, P.M. Ajayan, M.M. Rahman, Direct Ink Writing: A 3D Printing Technology for Diverse Materials, Advanced Materials 34 (2022). https://doi.org/10.1002/ADMA.202108855.

S.B. Balani, S.H. Ghaffar, M. Chougan, E. Pei, E. Şahin, Processes and materials used for direct writing technologies: A review, Results in Engineering 11 (2021) 100257. https://doi.org/10.1016/J.RINENG.2021.100257.

S.A. Khan, I. Lazoglu, Development of additively manufacturable and electrically conductive graphite–polymer composites, Progress in Additive Manufacturing 5 (2020) 153–162. https://doi.org/10.1007/s40964-019-00102-9.

L. del-Mazo-Barbara, M.P. Ginebra, Rheological characterisation of ceramic inks for 3D direct ink writing: A review, J Eur Ceram Soc 41 (2021) 18–33. https://doi.org/10.1016/J.JEURCERAMSOC.2021.08.031.

F. Abdeljawad, D.S. Bolintineanu, A. Cook, H. Brown-Shaklee, C. DiAntonio, D. Kammler, A. Roach, Sintering processes in direct ink write additive manufacturing: A mesoscopic modeling approach, Acta Mater 169 (2019) 60–75. https://doi.org/10.1016/J.ACTAMAT.2019.01.011.

S.A. Legett, X. Torres, A.M. Schmalzer, A. Pacheco, J.R. Stockdale, S. Talley, T. Robison, A. Labouriau, Balancing Functionality and Printability: High-Loading Polymer Resins for Direct Ink Writing, Polymers 2022, Vol. 14, Page 4661 14 (2022) 4661. https://doi.org/10.3390/POLYM14214661.

D. Graf, J. Jung, T. Hanemann, Formulation of a Ceramic Ink for 3D Inkjet Printing, Micromachines (Basel) 12 (2021). https://doi.org/10.3390/MI12091136.

Y. De Hazan, J. Heinecke, A. Weber, T. Graule, High solids loading ceramic colloidal dispersions in UV curable media via comb-polyelectrolyte surfactants, J Colloid Interface Sci 337 (2009) 66–74. https://doi.org/10.1016/J.JCIS.2009.05.012.

Z. Xing, W. Liu, Y. Chen, W. Li, Effect of plasticizer on the fabrication and properties of alumina ceramic by stereolithography-based additive manufacturing, Ceram Int 44 (2018) 19939–19944. https://doi.org/10.1016/J.CERAMINT.2018.07.259.

T. Chen, A. Sun, C. Chu, H. Wu, J. Wang, J. Wang, Z. Li, J. Guo, G. Xu, Rheological behavior of titania ink and mechanical properties of titania ceramic structures by 3D direct ink writing using high solid loading titania ceramic ink, J Alloys Compd 783 (2019) 321–328. https://doi.org/10.1016/J.JALLCOM.2018.12.334.

S. Gražulis, A. Daškevič, A. Merkys, D. Chateigner, L. Lutterotti, M. Quirós, N.R. Serebryanaya, P. Moeck, R.T. Downs, A. Le Bail, Crystallography Open Database (COD): An open-access collection of crystal structures and platform for world-wide collaboration, Nucleic Acids Res 40 (2012). https://doi.org/10.1093/NAR/GKR900.

J.I. Langford, X-ray diffraction procedures for polycrystalline and amorphous materials by H. P. Klug and L. E. Alexander, J Appl Crystallogr 8 (1975) 573–574. https://doi.org/10.1107/S0021889875011399.

D. Jung, S. Hwang, H.J. Kim, J.H. Han, H.N. Lee, Characterization of Porous CuO Films for H2S Gas Sensors, Materials 15 (2022) 7270. https://doi.org/10.3390/MA15207270/S1.

A. Shahzad, S.A. Khan, A. Paksoy, Ö. Balcı-Çağıran, I. Lazoglu, Negative additive manufacturing of Al2O3-Al cermet material by fused deposition and Direct Ink Writing, Mater Today Commun 33 (2022). https://doi.org/10.1016/J.MTCOMM.2022.104739.

D. Schroder, Semiconductor material and device characterization, IEEE Press; Wiley, Piscataway NJ; Hoboken N.J., 2006.