Углеродные нанотрубки для получения высокоэффективных электропроводящих композиционных материалов для аддитивного производства
DOI:
https://doi.org/10.24160/0013-5380-2026-7-81-88Ключевые слова:
токопроводящие полимерные композиты, нанокомпозиты, углеродные нанотрубки, аддитивное производствоАннотация
Статья посвящена созданию токопроводящих полимерных композиционных материалов для использования при LCD-печати с применением коммерческих фотополимерных смол и стандартных 3D-принтеров. Рассмотрены ключевые проблемы диспергирования углеродных нанотрубок в фотополимерных матрицах, обусловленные сильными Ван-дер-Ваальсовыми взаимодействиями и склонностью нанотрубок к агрегации. Проанализированы различные технологические приёмы получения проводящих композиций, включая механическое (высокоскоростное гомогенизирование, ультразвуковая обработка) и химическое диспергирование, применение поверхностно-активных веществ, растворителей, а также использование бинарных наполнителей. Проведена оценка электрофизических свойств полученных материалов по методикам ГОСТ и ASTM. Показано, что введение одностенных углеродных нанотрубок совместно с техническим углеродом позволяет достичь удельного объёмного электрического сопротивления 0,6–1,5 Ом‧м, тогда как по отдельности эти наполнители в исследуемом диапазоне концентраций не обеспечивают сопротивления менее 10⁷ Ом‧м. Установлено, что ключевыми факторами являются равномерность распределения наполнителя и стабильность суспензии. Результаты работы демонстрируют принципиальную возможность аддитивного производства токопроводящих изделий на стандартном оборудовании. Полученные данные могут быть использованы при разработке композитов для гибкой электроники, датчиков и систем электромагнитного экранирования.
Библиографические ссылки
1. Sun L. et al. Roles of Carbon Nanotubes in Novel Energy Storage Devices. – Carbon, 2017, vol. 122, pp. 462–474. DOI: 10.1016/j.carbon.2017.07.006.
2. Eletskii A. Sorption Properties of Carbon Nanostructures. – Physics-Uspekhi, 2004, vol. 47, No. 11, pp. 1119–1154. DOI: 10.1070/PU2004v047n11ABEH002017.
3. Girifalco L.A., Hodak M., Lee R.S. Carbon Nanotubes, Buckyballs, Ropes, and a Universal Graphitic Potential. – Physical Review B, 2000, vol. 62, No. 19, pp. 13104–13110. DOI: 10.1103/PhysRevB.62.13104.
4. Xie X.-L., Mai Y.-W., Zhou X.-P. Dispersion and Alignment of Carbon Nanotubes in Polymer Matrix: A Review. – Materials Science and Engineering: R: Reports, 2005, vol. 49, No. 4, pp. 89–112. DOI: 10.1016/j.mser.2005.04.002.
5. Yan Y. et al. Progress and Opportunities in Additive Manufacturing of Electrically Conductive Polymer Composites. – Materials Today Advances, 2023, vol. 17, DOI: 10.1016/j.mtadv.2022.100333.
6. Wiśniewska P. et al. Additive Manufacturing of Electrically Conductive Polymers: A Comprehensive Review. – Journal of Materials Chemistry C, 2025, vol. 13, pp. 21302–21332, DOI: 10.1039/D5TC02571K.
7. Tilve-Martinez D., Poulin P. Vat Photopolymerization 3D Printing of Conductive Nanocomposites. – Accounts of Materials Research, 2025, vol. 6, No. 5, pp. 661–671, DOI: 10.1021/accountsmr.5c00060.
8. Lu K.L. et al. Mechanical Damage of Carbon Nanotubes by Ultrasound. – Carbon, 1996, vol. 34, No. 6, pp. 814–816. DOI: 10.1016/0008-6223(96)89470-X.
9. Blake R. et al. A Generic Organometallic Approach Toward Ultra-Strong Carbon Nanotube Polymer Composites. – Journal of the American Chemical Society, 2004, vol. 126, No. 33, pp. 10226–10227. DOI: 10.1021/ja0474805.
10. Tasis D. et al. Soluble Carbon Nanotubes. – Chemistry –A European Journal, 2003, vol. 9, No. 17, pp. 4000–4008. DOI: 10.1002/chem.200304800.
11. Sanli A. et al. Effects of Different Types of Surfactant Treatments on the Electromechanical Properties of Multiwalled Carbon Nanotubes Decorated Electrospun Nanofibers. – Textile and Apparel, 2022, vol. 34, No. 11, pp. 11–18, DOI: 10.32710/tekstilvekonfeksiyon.1117280.
12. Inoue A.D. et al. Dispersion of Carbon Nanotubes Triggered by the Helical Self-Assembly of Poly(Methyl Methacrylate). – Nanoscale, 2025, vol. 17, pp. 18105–18111, DOI: 10.1039/D5NR01706H.
13. Jiang L.Q., Gao L., Sun J. Production of Aqueous Colloidal Dispersions of Carbon Nanotubes. – Journal of Colloid and Interface Science, 2003, vol. 260, No. 1, pp. 89–94. DOI: 10.1016/S0021-9797(02)00176-5.
14. Gong X. et al. Surfactant-Assisted Processing of Carbon Nanotube/Polymer Composites. – Chemistry of Materials, 2000, vol. 12, No. 4, pp. 1049–1052. DOI: 10.1021/cm9906396.
15. Chatterjee T. et al. Single-Walled Carbon Nanotube Dispersions in Poly (Ethylene Oxide). – Advanced Functional Materials, 2005, vol. 15, No. 11, pp. 1832–1838. DOI: 10.1002/adfm.200500290.
16. Patrick H.N., Warr G.G. Self-Assembly Structures of Nonionic Surfactants at Graphite–Solution Interfaces. 2. Effect of Polydispersity and Alkyl Chain Branching. – Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000, vol. 162, No. 1–3, pp. 149–157. DOI: 10.1016/S0927-7757(99)00187-9.
17. Yurekli K., Mitchell C.A., Krishnamoorti R. Small-Angle Neutron Scattering from Surfactant-Assisted Aqueous Dispersions of Carbon Nanotubes. – Journal of the American Chemical Society, 2004, vol. 126, No. 32, pp. 9902–9903. DOI: 10.1021/ja047451u.
18. Velasco-Santos C. et al. Dynamical–Mechanical and Thermal Analysis of Carbon Nanotube–Methyl-Ethyl Methacrylate Nano-composites. – Journal of Physics D: Applied Physics, 2003, vol. 36, No. 12, pp. 1423–1428. DOI: 10.1088/0022-3727/36/12/311.
19. Kim B., Lee J., Yu I. Electrical Properties of Single-Wall Carbon Nanotube and Epoxy Composites. – Journal of Applied Physics, 2003, vol. 94, No. 10, pp. 6724–6728. DOI: 10.1063/1.1622772.
20. Tan Y., Resasco D.E. Dispersion of Single-Walled Carbon Nanotubes of Narrow Diameter Distribution. – The Journal of Physical Chemistry B, 2005, vol. 109, No. 30, pp. 14454–14460. DOI: 10.1021/jp052217r.
21. Vaisman L., Marom G., Wagner H.D. Dispersions of Surface-Modified Carbon Nanotubes in Water-Soluble and Water-Insoluble Polymers. – Advanced Functional Materials, 2006, vol. 16, No. 3, pp. 357–363. DOI: 10.1002/adfm.200500142.
22. Strano M.S. et al. Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization. – Science, 2003, vol. 301, No. 5639, pp. 1519–1522. DOI: 10.1126/science.1087691.
23. Cheng F., Adronov A. Noncovalent Functionalization and Solubilization of Carbon Nanotubes by Using a Conjugated Zn–Porphyrin Polymer. – Chemistry – A European Journal, 2006, vol. 12, No. 19, pp. 5053–5059. DOI: 10.1002/chem.200600302.
24. Kaplan B. Synergistic Effects of Hybrid Single-Walled Carbon Nanotube/Carbon Black Fillers in 3D-Printable Polyamide 6 Nanocomposites: Balancing Electrical Conductivity and Mechanical Performance. – Polymer Engineering & Science, 2025, vol. 66, No. 1, pp. 364–377, DOI: 10.1002/pen.27192.
25. Saberi M. et al. Developing an Efficient Analytical Model for Predicting the Electrical Conductivity of Polymeric Nanocomposites Containing Hybrid Carbon Nanotube/Carbon Black Nanofillers. – Composites Part A: Applied Science and Manufacturing, 2024, vol. 185, DOI: 10.1016/j.compositesa.2024.108374.
26. Lee T. et al. Prediction of Curing Depth Dependence on CNT Nanofiller Dispersion for Vat Photopolymerization 3D Printing. – Chemical Engineering Journal, 2024, vol. 482, DOI: 10.2139/ssrn.4584399.
27. ГОСТ 20214-74. Пластмассы электропроводящие. Метод определения удельного объемного электрического сопротивления при постоянном напряжении. М.: Изд-во стандартов, 1974, 12 с.
28. ASTM F 1529-97. Standard Test Method for Sheet Resistance Uniformity Evaluation by in-Line Four-Point Probe with the Dual-Configuration Procedure. West Conshohocken, PA: ASTM International, 1997, 6 p.
---
Исследования проведены при реализации проекта «Разработка технологии получения наноструктурированных композиционных материалов нового поколения с низким удельным объемным электрическим сопротивлением и функциональных покрытий» в рамках федерального проекта «Университеты для поколения лидеров» национального проекта «Молодежь и дети»
#
1. Sun L. et al. Roles of Carbon Nanotubes in Novel Energy Storage Devices. – Carbon, 2017, vol. 122, pp. 462–474. DOI: 10.1016/ j.carbon.2017.07.006.
2. Eletskii A. Sorption Properties of Carbon Nanostructures. – Physics-Uspekhi, 2004, vol. 47, No. 11, pp. 1119–1154. DOI: 10.1070/PU2004v047n11ABEH002017.
3. Girifalco L.A., Hodak M., Lee R.S. Carbon Nanotubes, Buckyballs, Ropes, and a Universal Graphitic Potential. – Physical Review B, 2000, vol. 62, No. 19, pp. 13104–13110. DOI: 10.1103/PhysRevB.62.13104.
4. Xie X.-L., Mai Y.-W., Zhou X.-P. Dispersion and Alignment of Carbon Nanotubes in Polymer Matrix: A Review. – Materials Science and Engineering: R: Reports, 2005, vol. 49, No. 4, pp. 89–112. DOI: 10.1016/j.mser.2005.04.002.
5. Yan Y. et al. Progress and Opportunities in Additive Manufactu-ring of Electrically Conductive Polymer Composites. – Materials Today Advances, 2023, vol. 17, DOI: 10.1016/j.mtadv.2022.100333.
6. Wiśniewska P. et al. Additive Manufacturing of Electrically Conductive Polymers: A Comprehensive Review. – Journal of Materials Chemistry C, 2025, vol. 13, pp. 21302–21332, DOI: 10.1039/D5TC02571K.
7. Tilve-Martinez D., Poulin P. Vat Photopolymerization 3D Printing of Conductive Nanocomposites. – Accounts of Materials Research, 2025, vol. 6, No. 5, pp. 661–671, DOI: 10.1021/accountsmr.5c00060.
8. Lu K.L. et al. Mechanical Damage of Carbon Nanotubes by Ultrasound. – Carbon, 1996, vol. 34, No. 6, pp. 814–816. DOI: 10.1016/0008-6223(96)89470-X.
9. Blake R. et al. A Generic Organometallic Approach Toward Ultra-Strong Carbon Nanotube Polymer Composites. – Journal of the American Chemical Society, 2004, vol. 126, No. 33, pp. 10226–10227. DOI: 10.1021/ja0474805.
10. Tasis D. et al. Soluble Carbon Nanotubes. – Chemistry – A European Journal, 2003, vol. 9, No. 17, pp. 4000–4008. DOI: 10.1002/chem.200304800.
11. Sanli A. et al. Effects of Different Types of Surfactant Treatments on the Electromechanical Properties of Multiwalled Carbon Nanotubes Decorated Electrospun Nanofibers. – Textile and Apparel, 2022, vol. 34, No. 11, pp. 11–18, DOI: 10.32710/tekstilvekonfek-siyon.1117280.
12. Inoue A.D. et al. Dispersion of Carbon Nanotubes Triggered by the Helical Self-Assembly of Poly(Methyl Methacrylate). – Nano-scale, 2025, vol. 17, pp. 18105–18111, DOI: 10.1039/D5NR01706H.
13. Jiang L.Q., Gao L., Sun J. Production of Aqueous Colloidal Dispersions of Carbon Nanotubes. – Journal of Colloid and Interface Science, 2003, vol. 260, No. 1, pp. 89–94. DOI: 10.1016/S0021-9797(02)00176-5.
14. Gong X. et al. Surfactant-Assisted Processing of Carbon Nanotube/Polymer Composites. – Chemistry of Materials, 2000, vol. 12, No. 4, pp. 1049–1052. DOI: 10.1021/cm9906396.
15. Chatterjee T. et al. Single-Walled Carbon Nanotube Dispersions in Poly (Ethylene Oxide). – Advanced Functional Materials, 2005, vol. 15, No. 11, pp. 1832–1838. DOI: 10.1002/adfm.200500290.
16. Patrick H.N., Warr G.G. Self-Assembly Structures of Nonionic Surfactants at Graphite–Solution Interfaces. 2. Effect of Polydispersity and Alkyl Chain Branching. – Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000, vol. 162, No. 1–3, pp. 149–157. DOI: 10.1016/S0927-7757(99)00187-9.
17. Yurekli K., Mitchell C.A., Krishnamoorti R. Small-Angle Neutron Scattering from Surfactant-Assisted Aqueous Dispersions of Carbon Nanotubes. – Journal of the American Chemical Society, 2004, vol. 126, No. 32, pp. 9902–9903. DOI: 10.1021/ja047451u.
18. Velasco-Santos C. et al. Dynamical–Mechanical and Thermal Analysis of Carbon Nanotube–Methyl-Ethyl Methacrylate Nanocomposites. – Journal of Physics D: Applied Physics, 2003, vol. 36, No. 12, pp. 1423–1428. DOI: 10.1088/0022-3727/36/12/311.
19. Kim B., Lee J., Yu I. Electrical Properties of Single-Wall Carbon Nanotube and Epoxy Composites. – Journal of Applied Physics, 2003, vol. 94, No. 10, pp. 6724–6728. DOI: 10.1063/1.1622772.
20. Tan Y., Resasco D.E. Dispersion of Single-Walled Carbon Nanotubes of Narrow Diameter Distribution. – The Journal of Physical Chemistry B, 2005, vol. 109, No. 30, pp. 14454–14460. DOI: 10.1021/jp052217r.
21. Vaisman L., Marom G., Wagner H.D. Dispersions of Surface-Modified Carbon Nanotubes in Water-Soluble and Water-Insoluble Polymers. – Advanced Functional Materials, 2006, vol. 16, No. 3, pp. 357–363. DOI: 10.1002/adfm.200500142.
22. Strano M.S. et al. Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization. – Science, 2003, vol. 301, No. 5639, pp. 1519–1522. DOI: 10.1126/science.1087691.
23. Cheng F., Adronov A. Noncovalent Functionalization and Solubilization of Carbon Nanotubes by Using a Conjugated Zn–Porphyrin Polymer. – Chemistry – A European Journal, 2006, vol. 12, No. 19, pp. 5053–5059. DOI: 10.1002/chem.200600302.
24. Kaplan B. Synergistic Effects of Hybrid Single-Walled Carbon Nanotube/Carbon Black Fillers in 3D-Printable Polyamide 6 Nanocomposites: Balancing Electrical Conductivity and Mechanical Performance. – Polymer Engineering & Science, 2025, vol. 66, No. 1, pp. 364–377, DOI: 10.1002/pen.27192.
25. Saberi M. et al. Developing an Efficient Analytical Model for Predicting the Electrical Conductivity of Polymeric Nanocomposites Containing Hybrid Carbon Nanotube/Carbon Black Nanofillers. – Composites Part A: Applied Science and Manufacturing, 2024, vol. 185, DOI: 10.1016/j.compositesa.2024.108374.
26. Lee T. et al. Prediction of Curing Depth Dependence on CNT Nanofiller Dispersion for Vat Photopolymerization 3D Printing. – Chemical Engineering Journal, 2024, vol. 482, DOI: 10.2139/ssrn.4584399.
27. GOST 20214-74. Plastmassy elektroprovodyashchie. Metod opredeleniya udel’nogo ob’‘emnogo elektricheskogo soprotivleniya pri postoyannom napryazhenii (Plastics Are Electrically Conductive. Method for Determining the Specific Volume Electrical Resistance at Constant Voltage). M.: Izd-vo standartov, 1974, 12 p.
28. ASTM F 1529-97. Standard Test Method for Sheet Resistance Uniformity Evaluation by in-Line Four-Point Probe with the Dual-Configuration Procedure. West Conshohocken, PA: ASTM International, 1997, 6 p
---
The research was carried in the course of implementing the project "Development of Technology for the Production of New-Generation Nanostructured Composite Materials with Low Volume Electrical Resistivity and Functional Coatings" within the framework of the federal project "Universities for a Generation of Leaders" as part of the national project "Youth and Children"

