plasticnewsПластические массыPlasticheskie massy0554-2901PLASTMASSY Publishing House (Moscow)10.35164/0554-2901-2025-03-49-52plasticnews-1145Research ArticleПЕРЕРАБОТКАRECYCLINGИзменение молекулярных и термических характеристик термопластичного биоразлагаемого сополимера в FDM-процессеChange in molecular and thermal characteristics of thermoplastic biodegradable copolymer in FDM processКиселевЕ. Г.KiselevE. G.

660041; Красноярск

660041; Krasnoyarsk

evgeniygek@gmail.comДемиденкоА. В.DemidenkoA. V.

660041; Красноярск

660041; Krasnoyarsk

ВоловаТ. Г.VolovaT. G.

660041; Красноярск

660041; Krasnoyarsk

Институт биофизики СО РАН ФИЦ «Красноярский научный центр СО РАН»; Сибирский федеральный университетРоссияInstitute of Biophysics SB RAS FRC «Krasnoyarsk Sciencе Center SB RAS»; Siberian Federal UniversityRussian Federation202523072025034952Copyright © Киселев Е.Г., Демиденко А.В., Волова Т.Г., 20252025Киселев Е.Г., Демиденко А.В., Волова Т.Г.Kiselev E.G., Demidenko A.V., Volova T.G.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.plastics-news.ru/jour/article/view/1145

   Представлены результаты исследований и изменения молекулярно-массовых и термических свойств термопластичного сополимера микробиологического происхождения 3-гидроксибутирата-со-3-гидроксивалерата П(3ГБ-со-3ГВ) в многоэтапном процессе, включающем неоднократное плавление сополимера для получения гранул, экструзионного получения филаментов и собственно 3D-печати. В процессе получения гранулята, филаментов и FDM 3D-печати трехмерных образцов зафиксировано незначительное изменение температурных характеристик, включая температуры плавления и термической деструкции, кристаллизации и стеклования, а также заметное снижениемолекулярной массы (на 35 %). Зафиксированные изменения молекулярной массы и температурных характеристик сополимера П(3ГБ-со-3ГВ) в процессе переработки позволили получить филаменты для 3D-печати и напечатать 3D образцы, показатели которых соответствуют показателям для костно-пластических материалов и изделий.

   The results of studies and changes in the molecular weight and thermal properties of the thermoplastic copolymer of microbiological origin 3-hydroxybutyrate-co-3-hydroxyvalerate P(3HB-co-3HV) in a multi-stage process, including repeated melting of the copolymer to obtain pellets, extrusion production of filaments and 3D printing itself, are presented. In the process of obtaining granulate, filaments and FDM 3D printing of three-dimensional samples, a minor change in temperature characteristics was recorded, including melting and thermal destruction temperatures, crystallization and glass transition, as well as a noticeable decrease in molecular weight (by 35 %). The recorded changes in the molecular weight and temperature characteristics of the P(3HB-co-3HV) copolymer during processing made it possible to obtain fi laments for 3D printing and print 3D samples whose parameters correspond to those for bone-plastic materials and products.

сополимер 3-гидроксибутирата-со-3-гидроксивалератаП(3ГБ-со-3ГВ)переработка из расплавафиламентыFDM 3D-печатьмолекулярно-массовые и термические характеристики3-hydroxybutyrate-co-3-hydroxyvalerate copolymerP(3HB-co-3HB)melt processingfilamentsFDM 3D printingmolecular weight and thermal characteristicsИсследование выполнено в рамках государственного задания Министерства науки и высшего образования РФ (проект № FWES-2021-0025)The study was funded by State Assignment of the Ministry of Science and Higher Education of the Russian Federation (project No. FWES-2021-0025)ReferencesIslam A. Md., Mobarak H. Md., Rimon H. I. Md., Zobair Al Mahmu Md., Ghosh J., Ahmed S. M. Md., Hossain N. Additive manufacturing in polymer research: Advances, synthesis, and aррlications // Polymer Testing, 2024. N 132. P. 108364. DOI: 10.1016/j.polymertesting.2024.108364.Islam A. Md., Mobarak H. Md., Rimon H. I. Md., Zobair Al Mahmu Md., Ghosh J., Ahmed S. M. Md., Hossain N. Additive manufacturing in polymer research: Advances, synthesis, and aррlications // Polymer Testing, 2024. N 132. P. 108364. DOI: 10.1016/j.polymertesting.2024.108364.Alghamdi S.S., John S., Roy Choudhury N., Dutta N.K., Additive Manufacturing of Polymer Materials: Progress, Promise and Challenges // Polymers, 2021. N 13. P. 753. DOI: 10.3390/polym13050753.Alghamdi S.S., John S., Roy Choudhury N., Dutta N.K., Additive Manufacturing of Polymer Materials: Progress, Promise and Challenges // Polymers, 2021. N 13. P. 753. DOI: 10.3390/polym13050753.Sala D., Richert M. Perspectives of Additive Manufacturing in 5.0 Industry // Materials, 2025. N 18. P. 429. DOI: 10.3390/ma18020429.Sala D., Richert M. Perspectives of Additive Manufacturing in 5.0 Industry // Materials, 2025. N 18. P. 429. DOI: 10.3390/ma18020429.Yap Y.L., Tan Y.S. E., Tan H. K. J., Peh Z. K., Low X.Y., Yeong W.Y., Tan, C.S.H., Laude A. 3D printed bio-models for medical aррlications // Rapid Prototyping Journal. 2017. N 23 (2). P. 227–235. DOI: 10.1108/RPJ-08-2015-0102.Yap Y.L., Tan Y.S. E., Tan H. K. J., Peh Z. K., Low X.Y., Yeong W.Y., Tan, C.S.H., Laude A. 3D printed bio-models for medical aррlications // Rapid Prototyping Journal. 2017. N 23 (2). P. 227–235. DOI: 10.1108/RPJ-08-2015-0102.Scott C.S. Apparatus and Method for Creating Three-dimensional Objects Patent US 5121329-A, 29 November 1989.Scott C.S. Apparatus and Method for Creating Three-dimensional Objects Patent US 5121329-A, 29 November 1989.Joseph T.M., Kallingal A., Suresh A.M., Mahapatra D.K., Hasanin M.S., Haponiuk J., Thomas S. 3D printing of polylactic acid: recent advances and opportunities // International Journal of Advanced Manufacturing Technology, 2023. N 125. Pp. 1015–1035. DOI: 10.1007/s00170-022-10795-y.Joseph T.M., Kallingal A., Suresh A.M., Mahapatra D.K., Hasanin M.S., Haponiuk J., Thomas S. 3D printing of polylactic acid: recent advances and opportunities // International Journal of Advanced Manufacturing Technology, 2023. N 125. Pp. 1015–1035. DOI: 10.1007/s00170-022-10795-y.Tumer E.H., Erbil H.Y. Extrusion-Based 3D Printing applications of PLA Composites : A review // Coatings. 2021. N 11. P 390. DOI: 10.3390/coatings11040390.Tumer E.H., Erbil H.Y. Extrusion-Based 3D Printing applications of PLA Composites : A review // Coatings. 2021. N 11. P 390. DOI: 10.3390/coatings11040390.Dasgupta A., Dutta P. A Comprehensive Review on 3D Printing Technology: Current applications and Challenges // Jordan Journal of Mechanical and Industrial Engineering. 2022. N 16. Pp. 529–542. ISSN 1995-6665.Dasgupta A., Dutta P. A Comprehensive Review on 3D Printing Technology: Current applications and Challenges // Jordan Journal of Mechanical and Industrial Engineering. 2022. N 16. Pp. 529–542. ISSN 1995-6665.Bassand C., Benabed L., Charlon S., Verin J., Freitag J., Siepmann F., Soulestin J., Siepmann J. 3D printed PLGA implants: APF DDM vs. FDM // Journal of Controlled Release, 2023. N 353. Pp. 864–874. DOI: 10.1016/j.jconrel.2022.11.052Bassand C., Benabed L., Charlon S., Verin J., Freitag J., Siepmann F., Soulestin J., Siepmann J. 3D printed PLGA implants: APF DDM vs. FDM // Journal of Controlled Release, 2023. N 353. Pp. 864–874. DOI: 10.1016/j.jconrel.2022.11.052Kennedy S.W., Choudhury N.R., Parthasarathy R. 3D printing soft tissue scaffolds using Poly(caprolactone) // Bioprinting, 2023. N 30 (2). DOI: 10.1016/j.bprint.2023.e00259.Kennedy S.W., Choudhury N.R., Parthasarathy R. 3D printing soft tissue scaffolds using Poly(caprolactone) // Bioprinting, 2023. N 30 (2). DOI: 10.1016/j.bprint.2023.e00259.Moradi M., Beygi R., Yusof M.N., Ali Amiri A., da Silva L.F.M., Sharif S. 3D Printing of Acrylonitrile Butadiene Styrene by Fused Deposition Modeling: Artifi cial Neural Network and Response Surface Method Analyses // Journal of Materials Engineering and Performance, 2023. N32. Pp. 2016–2028. DOI: 10.1007/s11665-022-07250-0.Moradi M., Beygi R., Yusof M.N., Ali Amiri A., da Silva L.F.M., Sharif S. 3D Printing of Acrylonitrile Butadiene Styrene by Fused Deposition Modeling: Artifi cial Neural Network and Response Surface Method Analyses // Journal of Materials Engineering and Performance, 2023. N32. Pp. 2016–2028. DOI: 10.1007/s11665-022-07250-0.Zhou L., Miller J., Vezza J., Mayster M., Raffay M., Justice Q., Al Tamimi Z., Hansotte G., Sunkara L.D., Bernat J. Additive Manufacturing : A Comprehensive Review // Sensors, 2024. N 24, P. 2668. DOI: 10/3390/s24092668.Zhou L., Miller J., Vezza J., Mayster M., Raffay M., Justice Q., Al Tamimi Z., Hansotte G., Sunkara L.D., Bernat J. Additive Manufacturing : A Comprehensive Review // Sensors, 2024. N 24, P. 2668. DOI: 10/3390/s24092668.Koller M., Mukherjee A. A New Wave of Industrialization of PHA Biopolyesters // Bioengineering, 2022. N9. P. 74. DOI: 10.3390/bioengineering9020074.Koller M., Mukherjee A. A New Wave of Industrialization of PHA Biopolyesters // Bioengineering, 2022. N9. P. 74. DOI: 10.3390/bioengineering9020074.Laycock B., Halley P., Pratt S., Werker A., Lant P. The Chemomechanical Properties of Microbial Polyhydroxyalkanoates // Progress in Polymer Science, 2013. N 38, Pp. 536–583. DOI: 10.1016/j.progpolymsci.2012.06.003.Laycock B., Halley P., Pratt S., Werker A., Lant P. The Chemomechanical Properties of Microbial Polyhydroxyalkanoates // Progress in Polymer Science, 2013. N 38, Pp. 536–583. DOI: 10.1016/j.progpolymsci.2012.06.003.Volova T.G., Shishatskaya E.I., Sinskey A.J. Degradable Polymers: Production, Properties, applications – Nova Science Publishers, Inc., 2013.380 p.Volova T.G., Shishatskaya E.I., Sinskey A.J. Degradable Polymers: Production, Properties, applications – Nova Science Publishers, Inc., 2013.380 p.Mitra R., Xu T., Chen G., Xiang H., Han J. An Updated Overview on the Regulatory Circuits of Polyhydroxyalkanoates Synthesis // Microbial Biotechnology, 2022. N 15. Pp. 1446–1470. DOI: 10.1111/1751-7915.13915.Mitra R., Xu T., Chen G., Xiang H., Han J. An Updated Overview on the Regulatory Circuits of Polyhydroxyalkanoates Synthesis // Microbial Biotechnology, 2022. N 15. Pp. 1446–1470. DOI: 10.1111/1751-7915.13915.Choi S.Y., Lee Y., Yu H.E., Cho I.J., Kang M., Lee S.Y. Sustainable production and degradation of plastics using microbes // Nature Microbiology, 2023. N 8. Pp. 2253–2276. DOI: 10.1038/s41564-023-01529-1.Choi S.Y., Lee Y., Yu H.E., Cho I.J., Kang M., Lee S.Y. Sustainable production and degradation of plastics using microbes // Nature Microbiology, 2023. N 8. Pp. 2253–2276. DOI: 10.1038/s41564-023-01529-1.Asare E., Gregory D. A., Fricker A., Marcello E., Paxinou A., Taylor C.S., Haycock J.W., Roy I. Polyhydroxyalkanoates, Their Processing and Biomedical applications. In The Handbook of Polyhydroxyalkanoates – CRC Press: Boca Raton, FL, USA, 2020, Pp. 255–284. DOI: 10.1016/j.molmed.2022.01.007.Asare E., Gregory D. A., Fricker A., Marcello E., Paxinou A., Taylor C.S., Haycock J.W., Roy I. Polyhydroxyalkanoates, Their Processing and Biomedical applications. In The Handbook of Polyhydroxyalkanoates – CRC Press: Boca Raton, FL, USA, 2020, Pp. 255–284. DOI: 10.1016/j.molmed.2022.01.007.Rydz J., Sikorska W., Musioł M., Janeczek H., Włodarczyk J., Misiurska-Marczak M., Łęczycka J., Kowalczuk M. 3D-Printed Polyester-Based Prototypes for Cosmetic applications — Future Directions at the Forensic Engineering of Advanced Polymeric Materials // Materials 2019. N12. P. 994. DOI: 10.3390/ma120609994.Rydz J., Sikorska W., Musioł M., Janeczek H., Włodarczyk J., Misiurska-Marczak M., Łęczycka J., Kowalczuk M. 3D-Printed Polyester-Based Prototypes for Cosmetic applications — Future Directions at the Forensic Engineering of Advanced Polymeric Materials // Materials 2019. N12. P. 994. DOI: 10.3390/ma120609994.Интернет–магазин CollorFabb: официальный сайт. 2013. URL: https://colorfabb.com/catalogsearch/result/?q=pha (дата обращения: 30. 05. 2025).Интернет–магазин CollorFabb: официальный сайт. 2013. URL: https://colorfabb.com/catalogsearch/result/?q=pha (дата обращения: 30. 05. 2025).Gregory D.A., Fricker A.T.R., Mitrev P., Ray M., Asare E., Sim D., Larpnimitchai S., Zhang Z., Ma J., Tetali S.S.V. Additive Manufacturing of Polyhydroxyalkanoate-Based Blends Using Fused Deposition Modelling for the Development of Biomedical Devices // Journal of Functional Biomaterials, 2023. N 14. P. 40. DOI: 10.3390/jfb14010040.Gregory D.A., Fricker A.T.R., Mitrev P., Ray M., Asare E., Sim D., Larpnimitchai S., Zhang Z., Ma J., Tetali S.S.V. Additive Manufacturing of Polyhydroxyalkanoate-Based Blends Using Fused Deposition Modelling for the Development of Biomedical Devices // Journal of Functional Biomaterials, 2023. N 14. P. 40. DOI: 10.3390/jfb14010040.Kovalcik A., Sangroniz L., Kalina M., Skopalova K., Humpolíček P., Omastova M., Mundigler N., Müller A.J. Properties of Scaffolds Prepared by Fused Deposition Modeling of Poly(Hydroxyalkanoates) // International Journal of Biological Macromolecules, 2020. N 161. Pp. 364–376. DOI: 10.1016/j.ijbiomac.2020.06.022.Kovalcik A., Sangroniz L., Kalina M., Skopalova K., Humpolíček P., Omastova M., Mundigler N., Müller A.J. Properties of Scaffolds Prepared by Fused Deposition Modeling of Poly(Hydroxyalkanoates) // International Journal of Biological Macromolecules, 2020. N 161. Pp. 364–376. DOI: 10.1016/j.ijbiomac.2020.06.022.Wu C.S., Liao H.T. Interface Design of Environmentally Friendly Carbon Nanotube-Filled Polyester Composites: Fabrication, Characterisation, Functionality and application // Express Polymer Letter. 2017. N 11. Pp. 187–198. DOI: 10.3144/expresspolymlett.2017.20.Wu C.S., Liao H.T. Interface Design of Environmentally Friendly Carbon Nanotube-Filled Polyester Composites: Fabrication, Characterisation, Functionality and application // Express Polymer Letter. 2017. N 11. Pp. 187–198. DOI: 10.3144/expresspolymlett.2017.20.Wu C.-S., Liao H.-T., Cai Y.-X. Characterisation, Biodegradability and application of Palm Fibre-Reinforced Polyhydroxyalkanoate Composites // Polymer Degradation Stability, 2017. N 140. Pp. 55–63. DOI: 10.1016/j.polymdegradstab.2017.04.016.Wu C.-S., Liao H.-T., Cai Y.-X. Characterisation, Biodegradability and application of Palm Fibre-Reinforced Polyhydroxyalkanoate Composites // Polymer Degradation Stability, 2017. N 140. Pp. 55–63. DOI: 10.1016/j.polymdegradstab.2017.04.016.Duan B., Cheung W.L., Wang M. Optimized Fabrication of Ca–P/PHBV Nanocomposite Scaffolds via Selective Laser Sintering for Bone Tissue Engineering // Biofabrication, 2011. N 3. P. 015001. DOI: 10.1088/1758-5082/3/1/01500124.Duan B., Cheung W.L., Wang M. Optimized Fabrication of Ca–P/PHBV Nanocomposite Scaffolds via Selective Laser Sintering for Bone Tissue Engineering // Biofabrication, 2011. N 3. P. 015001. DOI: 10.1088/1758-5082/3/1/01500124.Puppi D., Pirosa A., Morelli A., Chiellini F. Design, Fabrication and Characterization of Tailored Poly[(R)-3-Hydroxybutyrate-Co-(R)-3-Hydroxyexanoate] Scaff olds by Computer-Aided Wet-Spinning // Rapid Prototyping Journal. 2018. N 24. Pp. 1–8. DOI: 10.1108/RPJ-03-2016-0037.Puppi D., Pirosa A., Morelli A., Chiellini F. Design, Fabrication and Characterization of Tailored Poly[(R)-3-Hydroxybutyrate-Co-(R)-3-Hydroxyexanoate] Scaff olds by Computer-Aided Wet-Spinning // Rapid Prototyping Journal. 2018. N 24. Pp. 1–8. DOI: 10.1108/RPJ-03-2016-0037.Патент РФ No. 2439143 Российская федерация МПК C12N 1/20 (2006.01) C12P 7/62 (2006.01). Штамм бактерий ВКПМ В-10646 – продуцент полигидроксиалканоатов и способ их получения: № 2010146514/10: заявл. 15. 11. 2010: опубл. 10. 01. 2012 / Волова Т.Г., Шишацкая Е. И.: заявитель Волова Т.Г., Шишацкая Е.И. – 13 с.Патент РФ No. 2439143 Российская федерация МПК C12N 1/20 (2006.01) C12P 7/62 (2006.01). Штамм бактерий ВКПМ В-10646 – продуцент полигидроксиалканоатов и способ их получения: № 2010146514/10: заявл. 15. 11. 2010: опубл. 10. 01. 2012 / Волова Т.Г., Шишацкая Е. И.: заявитель Волова Т.Г., Шишацкая Е.И. – 13 с.Volova T., Kiselev E., Vinogradova O., Nikolaeva E., Chistyakov A., Sukovatiy A., Shishatskaya E. A Glucose-Utilizing Strain, Cupriavidus Euthrophus B-10646: Growth Kinetics, Characterization and Synthesis of Multicomponent PHAs // PLoS ONE. 2014. N 9. DOI: 10.1371/journal.pone.0087551.Volova T., Kiselev E., Vinogradova O., Nikolaeva E., Chistyakov A., Sukovatiy A., Shishatskaya E. A Glucose-Utilizing Strain, Cupriavidus Euthrophus B-10646: Growth Kinetics, Characterization and Synthesis of Multicomponent PHAs // PLoS ONE. 2014. N 9. DOI: 10.1371/journal.pone.0087551.Braunegg G., Sonnleitner B., Lafferty R. M. A Rapid Gas Chromatographic Method for the Determination of Poly-β-Hydroxybutyric Acid in Microbial Biomass // European journal of applied microbiology and biotechnology, 1978. N 6. Pp. 29–37. DOI: 10.1007/bf00500854/Braunegg G., Sonnleitner B., Lafferty R. M. A Rapid Gas Chromatographic Method for the Determination of Poly-β-Hydroxybutyric Acid in Microbial Biomass // European journal of applied microbiology and biotechnology, 1978. N 6. Pp. 29–37. DOI: 10.1007/bf00500854/Патент РФ No. 2769197 Российская федерация МПК B29C 48/88 (2019.01). Устройство завихрителя потоков воздуха для охлаждения экструдированных масс.: № 2020118611: заявл. 27. 05. 2020: опубл.: 29. 03. 2022 / Кистерский K.А : заявитель ФГАОУ ВО СФУ. – 7 с.Патент РФ No. 2769197 Российская федерация МПК B29C 48/88 (2019.01). Устройство завихрителя потоков воздуха для охлаждения экструдированных масс.: № 2020118611: заявл. 27. 05. 2020: опубл.: 29. 03. 2022 / Кистерский K.А : заявитель ФГАОУ ВО СФУ. – 7 с.Shishatskaya E.I., Demidenko A.V., Sukovatyi A.G., Dudaev A.E., Mylnikov A.V., Kisterskiy K.A., Volova T.G. 3D printing of poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] biodegradable scaffolds: properties, in vitro and in vivo evaluation // International Journal of Molecular Sciences. 2023. N 24(16). Pp. 12969–1289. DOI: 10.3390/ijms241612969.Shishatskaya E.I., Demidenko A.V., Sukovatyi A.G., Dudaev A.E., Mylnikov A.V., Kisterskiy K.A., Volova T.G. 3D printing of poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] biodegradable scaffolds: properties, in vitro and in vivo evaluation // International Journal of Molecular Sciences. 2023. N 24(16). Pp. 12969–1289. DOI: 10.3390/ijms241612969.

The authors declare that there are no conflicts of interest present.