Applied Chemical Engineering

Spectroscopic Fingerprinting of Polymers in FDM-AM: FTIR and Raman Insights into Degradation Pathways

Gufran Yassin Abass Hussain

Medical Devices Engineering Technology, Al-Turath University, Baghdad,10013, Iraq

Raghad Saad Majeed

Medical Technical College, Al-Farahidi University, Baghdad,10111, Iraq

Abdul_mohsen Naji Al-mohesen

Al-Hadi University College, Baghdad, 10011, Iraq

Issa Mohammed Kadhim

Department of Medical Laboratories Technology, Al-Nisour University College, Nisour Seq. Karkh, Baghdad,10015,Iraq

Muntadher Abed Hussein

Al-Manara College For Medical Sciences, Amarah, Maysan, 62001/Iraq

Nour Mohamd Rasla

Department of Medicinal Chemistry, Al-Zahrawi University College, Karbala,56001, Iraq.

Amran Mezher Lawas

Department of Medicinal Chemistry, Mazaya University College, Dhi Qar,21974, Iraq.

Duha Abed Almuhssen Muzahim

Department of Medicinal Chemistry, Mazaya University College, Dhi Qar,21974, Iraq.

Heba Khaled Zubairi

College of Health and Medical Techniques, AL-Bayan University, Baghdad, Iraq.

DOI: https://doi.org/10.59429/ace.v8i4.5744

Keywords: Additive manufacturing; fused deposition modeling; ftir spectroscopy; raman spectroscopy; polymer degradation; recycling

---

Abstract

Fused deposition modeling additive manufacturing (FDM-AM) has emerged as one of the most widely adopted techniques for fabricating polymer-based functional components. However, polymers used in FDM-AM are prone to degradation during thermal processing, extrusion, and repeated recycling, which compromises their performance and lifespan. Spectroscopic methods, particularly Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy, provide non-destructive and highly sensitive tools for fingerprinting polymers and monitoring their degradation pathways. This work presents a comprehensive analysis of how FTIR and Raman spectral signatures can be employed to identify thermal, oxidative, and hydrolytic degradation in commonly used FDM polymers such as PLA, ABS, PETG, and Nylon. The correlation between vibrational bands and chemical transformations—such as chain scission, cross-linking, and formation of carbonyl or hydroxyl functionalities—is discussed in detail. Furthermore, the study outlines a spectroscopic protocol for tracking recycling-induced changes and highlights the complementary role of FTIR and Raman in capturing subtle molecular-level variations. The proposed insights establish spectroscopy as a reliable diagnostic tool for quality assurance, recycling feasibility, and material selection in polymer additive manufacturing.

---

References

[1]. Üstündağ, M. (2025). The Transformative Role of Additive Manufacturing: Current Innovations, Applications, and Future Directions Across Industries. Duzce University Journal of Science and Technology, 13(2), 942-963.

[2]. Subramani, R. (2025). Optimizing process parameters for enhanced mechanical performance in 3D printed impellers using graphene-reinforced polylactic acid (G-PLA) filament. Journal of Mechanical Science and Technology, 1-11.

[3]. Raja, S., Murali, A. P., & Praveenkumar, V. (2024). Tailored microstructure control in Additive Manufacturing: Constant and varying energy density approach for nickel 625 superalloy. Materials Letters, 375, 137249.

[4]. Subramani Raja, Ahamed Jalaludeen Mohammad Iliyas, Paneer Selvam Vishnu, Amaladas John Rajan, Maher Ali Rusho, Mohamad Reda Refaa, Oluseye Adewale Adebimpe. Sustainable manufacturing of FDM-manufactured composite impellers using hybrid machine learning and simulation-based optimization. Materials ScienceinAdditive Manufacturing 2025, 4(3), 025200033. https://doi.org/10.36922/MSAM025200033

[5]. Aarthi, S., Subramani, R., Rusho, M. A., Sharma, S., Ramachandran, T., Mahapatro, A., & Ismail, A. I. (2025). Genetically engineered 3D printed functionally graded-lignin, starch, and cellulose-derived sustainable biopolymers and composites: A critical review. International Journal of Biological Macromolecules, 145843.

[6]. Lazarus, B., Raja, S., Shanmugam, K., & Yishak, S. (2024). Analysis and Optimization of Thermoplastic Polyurethane Infill Patterns for Additive Manufacturing in Pipeline Applications.

[7]. Kumar, J. V., Radhakrishnan, K., & Priya, L. S. (2025). Shaping Tomorrow: The Impact of 3D Printing on Functional Material Fabrication. In Breaking Boundaries: Pioneering Sustainable Solutions Through Materials and Technology (pp. 281-306). Singapore: Springer Nature Singapore.

[8]. Subramani, R., Leon, R. R., Nageswaren, R., Rusho, M. A., & Shankar, K. V. (2025). Tribological Performance Enhancement in FDM and SLA Additive Manufacturing: Materials, Mechanisms, Surface Engineering, and Hybrid Strategies—A Holistic Review. Lubricants, 13(7), 298.

[9]. Mallikarjuna, B., Bhargav, P., Hiremath, S., Jayachristiyan, K. G., & Jayanth, N. (2025). A review on the melt extrusion-based fused deposition modeling (FDM): background, materials, process parameters and military applications. International Journal on Interactive Design and Manufacturing (IJIDeM), 19(2), 651-665.

[10]. Kantaros, A., Katsantoni, M., Ganetsos, T., & Petrescu, N. (2025). The evolution of thermoplastic raw materials in high-speed FFF/FDM 3D printing era: challenges and opportunities. Materials, 18(6), 1220.

[11]. Mallikarjuna, B., Bhargav, P., Hiremath, S., Jayachristiyan, K. G., & Jayanth, N. (2025). A review on the melt extrusion-based fused deposition modeling (FDM): background, materials, process parameters and military applications. International Journal on Interactive Design and Manufacturing (IJIDeM), 19(2), 651-665.

[12]. Nesheim, O. S., Cao, A., Ducarouge, L., & Elverum, C. W. (2025). Improved out-of-plane properties through alternative print path and in-layer heating. Virtual and Physical Prototyping, 20(1), e2521106.

[13]. Mohammed Ahmed Mustafa, S. Raja, Layth Abdulrasool A. L. Asadi, Nashrah Hani Jamadon, N. Rajeswari, Avvaru Praveen Kumar, "A Decision-Making Carbon Reinforced Material Selection Model for Composite Polymers in Pipeline Applications", Advances in Polymer Technology, vol. 2023, Article ID 6344193, 9 pages, 2023. https://doi.org/10.1155/2023/6344193

[14]. Olaiya, N. G., Maraveas, C., Salem, M. A., Raja, S., Rashedi, A., Alzahrani, A. Y., El-Bahy, Z. M., & Olaiya, F. G. (2022). Viscoelastic and Properties of Amphiphilic Chitin in Plasticised Polylactic Acid/Starch Biocomposite. Polymers, 14(11), 2268. https://doi.org/10.3390/polym14112268

[15]. Praveenkumar, V., Raja, S., Jamadon, N. H., & Yishak, S. (2023). Role of laser power and scan speed combination on the surface quality of additive manufactured nickel-based superalloy. Proceedings of the Institution of Mechanical Engineers, Part L: Journal of Materials: Design and Applications, 14644207231212566.

[16]. S., Aarthi, S., Raja, Rusho, Maher Ali, Yishak, Simon, Bridging Plant Biotechnology and Additive Manufacturing: A Multicriteria Decision Approach for Biopolymer Development, Advances in Polymer Technology, 2025, 9685300, 24 pages, 2025. https://doi.org/10.1155/adv/9685300

[17]. Liang, Y., Wei, X., Peng, Y., Wang, X., & Niu, X. (2025). A review on recent applications of machine learning in mechanical properties of composites. Polymer Composites, 46(3), 1939-1960.

[18]. Rivera-Rivera, D. M., Quintanilla-Villanueva, G. E., Luna-Moreno, D., Sánchez-Álvarez, A., Rodríguez-Delgado, J. M., Cedillo-González, E. I., ... & Rodríguez-Delgado, M. M. (2025). Exploring Innovative Approaches for the Analysis of Micro-and Nanoplastics: Breakthroughs in (Bio) Sensing Techniques. Biosensors, 15(1), 44.

[19]. Selvaraj, V. K., Subramanian, J., Krishna Rajeev, P., Rajendran, V., & Raja, S. Optimization of conductive nanofillers in bio‐based polyurethane foams for ammonia‐sensing application. Polymer Engineering & Science.

[20]. Theng, A. A. S., Jayamani, E., Subramanian, J., Selvaraj, V. K., Viswanath, S., Sankar, R., ... & Rusho, M. A. (2025). A review on industrial optimization approach in polymer matrix composites manufacturing. International Polymer Processing.

[21]. Long, J., Nand, A., & Ray, S. (2021). Application of spectroscopy in additive manufacturing. Materials, 14(1), 203.

[22]. Cuiffo, M. A., Snyder, J., Elliott, A. M., Romero, N., Kannan, S., & Halada, G. P. (2017). Impact of the fused deposition (FDM) printing process on polylactic acid (PLA) chemistry and structure. Applied Sciences, 7(6), 579.

[23]. Haryńska, A., Janik, H., Sienkiewicz, M., Mikolaszek, B., & Kucińska-Lipka, J. (2021). PLA–potato thermoplastic starch filament as a sustainable alternative to the conventional PLA filament: Processing, characterization, and FFF 3D printing. ACS Sustainable Chemistry & Engineering, 9(20), 6923-6938.

[24]. Dangnan, F., Espejo, C., Liskiewicz, T., Gester, M., & Neville, A. (2021). Water barrier performance of additively manufactured polymers coated with diamond-like carbon films. Diamond and Related Materials, 119, 108541.

[25]. Subramani, R., Vijayakumar, P., Rusho, M. A., Kumar, A., Shankar, K. V., & Thirugnanasambandam, A. K. (2024). Selection and Optimization of Carbon-Reinforced Polyether Ether Ketone Process Parameters in 3D Printing—A Rotating Component Application. Polymers, 16(10), 1443.

[26]. Osamah Sabah Barrak, Mahmood Mohammed Hamzah, Ali Safaa Ali, Slim Ben-Elechi, Sami Chatti, Wasaq Haider Moubder, … Arfan Ali Ahmad. (2023). Joining of Polymer to Aluminum Alloy AA1050 By Friction Spot Welding. Journal of Techniques, 5(4), 88–94. https://doi.org/10.51173/jt.v5i4.1976.

[27]. Subramani, R., Kaliappan, S., Arul, P. V, Sekar, S., Poures, M. V. De, Patil, P. P., & Esakki, E. S. (2022). A Recent Trend on Additive Manufacturing Sustainability with Supply Chain Management Concept , Multicriteria Decision Making Techniques. 2022.

[28]. Pezzana, L. (2024). Towards a more sustainable world: UV-curing & 3D printing of bio-based monomers: Synthesis and characterization of bio-derived monomers for cationic and radical UV-curing.

[29]. Bharat, N., Mishra, V., Veeman, D., Kumar, V., & Setia, G. (2025). Structural and mechanical performance of material extrusion-based 3D printed PLA/Lawsonia inermis composite. Wood Material Science & Engineering, 1-15.

[30]. Raja, S., Mustafa, M. A., Ghadir, G. K., Al-Tmimi, H. M., Alani, Z. K., Rusho, M. A., & Rajeswari, N. (2024). Unlocking the potential of polymer 3D printed electronics: Challenges and solutions. Applied Chemical Engineering, 7(2), 3877-3877.

[31]. Zhang, Y., Xu, Y., Song, Y., & Zheng, Q. (2013). Study of poly (vinyl chloride)/acrylonitrile–styrene–acrylate blends for compatibility, toughness, thermal stability and UV irradiation resistance. Journal of Applied Polymer Science, 130(3), 2143-2151.

[32]. Saviello, D., Pouyet, E., Toniolo, L., Cotte, M., & Nevin, A. (2014). Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile–butadiene–styrene model samples and historical objects. Analytica Chimica Acta, 843, 59-72.

[33]. Kister, G., Cassanas, G., & Vert, M. (1998). Effects of morphology, conformation and configuration on the IR and Raman spectra of various poly (lactic acid) s. Polymer, 39(2), 267-273.

[34]. Subramani, R., Ali, R. M., Surakasi, R., Sudha, D. R., Karthick, S., Karthikeyan, S., ... & Selvaraj, V. K. (2024). Surface metamorphosis techniques for sustainable polymers: Optimizing material performance and environmental impact. Applied Chemical Engineering, 7(3), 11-11.

[35]. Liubimovskii, S. O., Novikov, V. S., Vasimov, D. D., Kuznetsov, S. M., Sagitova, E. A., Dmitryakov, P. V., ... & Nikolaeva, G. Y. (2024). Raman evaluation of the crystallinity degree of poly (L-Lactide)-based materials. Physics of Wave Phenomena, 32(2), 140-149.

[36]. Hsu, S. L., & Yang, X. (2021). Spectroscopic Analysis of Structural Transformations Associated with Poly (lactic acid). Spectroscopic Techniques for Polymer Characterization: Methods, Instrumentation, Applications, 317-344.

[37]. Verbeek, C. J. R., & Bier, J. M. (2011). Synthesis and characterization of thermoplastic agro-polymers.

[38]. Gupta, A., Patel, P., Shah, S., & Patel, K. (2025). Nanocomposites in focus: tailoring drug delivery for enhanced therapeutic outcomes. Future Journal of Pharmaceutical Sciences, 11(1), 37.

[39]. Liu, Y. (2020). In-operando X-ray analysis of temperature-responsive changes in layered structure of polymer ultrathin films. (No Title).

[40]. Chen, C. T., & Peng, R. C. (2021). Design and 3D printing of paper-based shape memory polymer actuated for soft lightweight fingers. Smart Materials and Structures, 30(7), 075010.

[41]. Subramani, R., Kaliappan, S., Sekar, S., Patil, P. P., Usha, R., Manasa, N., & Esakkiraj, E. S. (2022). Polymer Filament Process Parameter Optimization with Mechanical Test and Morphology Analysis. 2022.

[42]. Subramani, R., & Yishak, S. (2024). Utilizing Additive Manufacturing for Fabricating Energy Storage Components From Graphene‐Reinforced Thermoplastic Composites. Advances in Polymer Technology, 2024(1), 6464049.

[43]. Raja, S., Ali, R. M., Babar, Y. V., Surakasi, R., Karthikeyan, S., Panneerselvam, B., & Jagadheeswari, A. S. (2024). Integration of nanomaterials in FDM for enhanced surface properties: Optimized manufacturing approaches. Applied Chemical Engineering, 7(3).

[44]. Subramani, R., Mustafa, M. A., Ghadir, G. K., Al-Tmimi, H. M., Alani, Z. K., Rusho, M. A., ... & Kumar, A. P. (2024). Advancements in 3D printing materials: A comparative analysis of performance and applications. Applied Chemical Engineering, 3867-3867.

[45]. Selvaraj, V. K., Subramanian, J., Lazar, P., Raja, S., Jafferson, J. M., Jeevan, S., ... & Zachariah, A. A. (2024, February). An Experimental and Optimization of Bio-Based Polyurethane Foam for Low-Velocity Impact: Towards Futuristic Applications. In International Conference on Advanced Materials Manufacturing and Structures (pp. 244-261). Cham: Springer Nature Switzerland.