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Polymers
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3D Printing of Polymer Materials: Recent Advances and Future Perspectives
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3D Printing of Polymer Materials: Recent Advances and Future Perspectives

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Processing and Engineering".

Deadline for manuscript submissions: 20 September 2024 | Viewed by 4872

Special Issue Editors

Dr. Michael A. Smirnov

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Guest Editor
Institute of Macromolecular Compounds, Russian Academy of Sciences, V.O. Bolshoi Pr. 31, 199004 St. Petersburg, Russia
Interests: 3D printing; polymer chemistry; physical chemistry of polymer materials; electroactive polymers; polymer electrochemistry; carbohydrate polymers; deep eutectic solvents; polymer composites; ionic liquids; polymer ion gels
Dr. Maria P. Sokolova

E-Mail Website1 Website2
Guest Editor
Institute of Macromolecular Compounds, Russian Academy of Sciences, V.O. Bolshoi Pr. 31, 199004 St. Petersburg, Russia
Interests: atomic force microscopy; scanning and transmission electron microscopy; X-ray diffraction analysis; structure of polymers; nano- and microstructures; carbohydrate polymeric materials; composite materials; deep eutectic solvents

Special Issue Information

Dear Colleagues,

The 3D printing of polymer materials is an intensively developed technology intended for the preparation of complex shaped materials with various mechanical properties.  In spite of significant progress in 3D printing, obtaining advanced polymer materials such as composites, materials with ultimate mechanical or tailored functional properties, remains a challenge. Among others, polymer gels (“soft materials”) are subject to intensive study because they are often capable of mimicking the mechanical behavior of natural tissues and objects. Due to the opening of new opportunities for customization and personalization of products in the field of biomaterials, robotics, food science and technology, cell tissue engineering, and others, the development of production methods for polymer gels with arbitrary geometries has attracted significant attention in previous years. Inks applied for this process consist of artificial or natural polymers compatible with the used solvent, which is usually water. New types of solvents, namely ionic liquids and deep eutectic solvents, are also studied in the context of the elaboration of compositions with improved printability.

The main avenue of research on the way toward better printable compositions is the interplay between their rheological characteristics, which determine the printing performance and mechanical properties of the final material. In the case of gels, the problem of shape fidelity arises because of their slow structure recovery after extrusion and possible solvent evaporation. Additionally, the physico-chemical and often biological properties of printed materials should be taken into account, and this narrows the choice of possible components of printable composition. The chemical challenge is the elaboration of new shape fixation methods for gels via a suitable physical or chemical crosslinking process that meet the requirements of subsequent applications of the printed material, and the investigation of the influence of this process on the functional properties of the obtained gel product. New printing and curing strategies are also needed in order to achieve better interlayer adhesiveness and improve the mechanical characteristics of end products.

This Special Issue welcomes (but is not limited to) papers on 3D printing of polymer materials based on a wide range of synthetic or natural polymers, including theoretical and experimental studies of their rheological properties, crosslinking, and printing accuracy, as well as investigations of practical applications of 3D printed polymer materials.       

Dr. Michael A. Smirnov
Dr. Maria P. Sokolova
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • 3D printing
  • additive manufacturing
  • printing accuracy
  • polymer materials
  • composites
  • polymer gels
  • rheology
  • crosslinking
  • properties of materials

Published Papers (5 papers)

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19 pages, 5627 KiB  
Article
Precisely Printable Silk Fibroin/Carboxymethyl Cellulose/Alginate Bioink for 3D Printing
by Yuliya Nashchekina, Anastasia Militsina, Vladimir Elokhovskiy, Elena Ivan’kova, Alexey Nashchekin, Almaz Kamalov and Vladimir Yudin
Polymers 2024, 16(8), 1027; https://doi.org/10.3390/polym16081027 - 09 Apr 2024
Viewed by 545
Abstract
Three-dimensional (3D) bioprinting opens up many possibilities for tissue engineering, thanks to its ability to create a three-dimensional environment for cells like an extracellular matrix. However, the use of natural polymers such as silk fibroin in 3D bioprinting faces obstacles such as having [...] Read more.
Three-dimensional (3D) bioprinting opens up many possibilities for tissue engineering, thanks to its ability to create a three-dimensional environment for cells like an extracellular matrix. However, the use of natural polymers such as silk fibroin in 3D bioprinting faces obstacles such as having a limited printability due to the low viscosity of such solutions. This study addresses these gaps by developing highly viscous, stable, and biocompatible silk fibroin-based inks. The addition of 2% carboxymethyl cellulose sodium and 1% sodium alginate to an aqueous solution containing 2.5 to 5% silk fibroin significantly improves the printability, stability, and mechanical properties of the printed scaffolds. It has been demonstrated that the more silk fibroin there is in bioinks, the higher their printability. To stabilize silk fibroin scaffolds in an aqueous environment, the printed structures must be treated with methanol or ethanol, ensuring the transition from the silk fibroin’s amorphous phase to beta sheets. The developed bioinks that are based on silk fibroin, alginate, and carboxymethyl cellulose demonstrate an ease of printing and a high printing quality, and have a sufficiently good biocompatibility with respect to mesenchymal stromal cells. The printed scaffolds have satisfactory mechanical characteristics. The resulting 3D-printing bioink composition can be used to create tissue-like structures. Full article
(This article belongs to the Special Issue 3D Printing of Polymer Materials: Recent Advances and Future Perspectives)
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19 pages, 3949 KiB  
Article
The Influence of Selected Fillers on the Functional Properties of Polycarbonate Dedicated to 3D Printing Applications
by Katarzyna Bulanda, Mariusz Oleksy and Rafał Oliwa
Polymers 2024, 16(5), 592; https://doi.org/10.3390/polym16050592 - 21 Feb 2024
Viewed by 748
Abstract
Additive manufacturing is still the fastest-developing technology in the modern world. Three-dimensional printing has become popular due to the method’s numerous advantages, such as its short time and low cost, compared to conventional methods such as injection molding. Therefore, the demand for new [...] Read more.
Additive manufacturing is still the fastest-developing technology in the modern world. Three-dimensional printing has become popular due to the method’s numerous advantages, such as its short time and low cost, compared to conventional methods such as injection molding. Therefore, the demand for new materials and material systems that will be characterized by the desired functional properties is clearly growing. As part of this work, work was carried out on the development and preparation of new polymer composites dedicated to 3D printing applications, especially in FDM/FFF/MEM technologies. The influence of the content and amount of fillers, such as silica modified with alumina (S) and bentonite modified with a quaternary ammonium salt (B), on the functional properties of a commercially available fiber made of traditional plastic, such as polycarbonate, obtained in the form of a filament (PCF), was determined. It was found that the addition of B significantly increased the fluidity of the polymer, the introduction of a filler in the amount of 1.5% allowed to obtain a result that was 6% higher compared to PCF (16.8 g/10 min), while the amount of 3% was 20% higher. The obtained mass melt flow rate (MFR) results were confirmed by determining the viscosity of the produced polymer composites. Satisfactory results of mechanical properties were obtained, including the following: it was found that the introduced modified fillers increased the elasticity of the material. The introduction of modified silica resulted in a reduction in Young’s modulus by 10.02% at the content of 0.5% S and at 1% S by 8.64% compared to the polymer. The introduced modified filler S significantly increased the thermostability of polycarbonate (T5% equal to 449 °C) by 23 °C for PCF/0.5% S and 14 °C for PCF/1% S, respectively. The SEM and WAXS results confirmed the appropriate dispersion of the fillers in the polymer matrix, which indicates well-selected conditions for the homogenization process of the components and the subsequent production of samples. Detailed characterization of the influence of selected fillers on the functional properties of the polymer matrix-polycarbonate allowed for an increase in the range of polymer composites and their use in rapid prototyping technologies, as well as supplementing the literature on databases regarding the characteristics of the obtained materials. Full article
(This article belongs to the Special Issue 3D Printing of Polymer Materials: Recent Advances and Future Perspectives)
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24 pages, 8460 KiB  
Article
Drug Loaded 3D-Printed Poly(ε-Caprolactone) Scaffolds for Local Antibacterial or Anti-Inflammatory Treatment in Bone Regeneration
by Mariia Stepanova, Ilia Averianov, Iosif Gofman, Natalia Shevchenko, Artem Rubinstein, Tatiana Egorova, Andrey Trulioff, Yulia Nashchekina, Igor Kudryavtsev, Elena Demyanova, Evgenia Korzhikova-Vlakh and Viktor Korzhikov-Vlakh
Polymers 2023, 15(19), 3957; https://doi.org/10.3390/polym15193957 - 30 Sep 2023
Cited by 3 | Viewed by 1263
Abstract
Annual bone grafting surgeries due to bone fractures, resections of affected bones, skeletal anomalies, osteoporosis, etc. exceed two million worldwide. In this regard, the creation of new materials for bone tissue repair is one of the urgent tasks of modern medicine. Additive manufacturing, [...] Read more.
Annual bone grafting surgeries due to bone fractures, resections of affected bones, skeletal anomalies, osteoporosis, etc. exceed two million worldwide. In this regard, the creation of new materials for bone tissue repair is one of the urgent tasks of modern medicine. Additive manufacturing, or 3D printing, offers great opportunities for the development of materials with diverse properties and designs. In this study, the one-pot technique for the production of 3D scaffolds based on poly(ε-caprolactone) (PCL) loaded with an antibiotic or anti-inflammatory drug was proposed. In contrast to previously described methods to prepare drug-containing scaffolds, drug-loaded PCL scaffolds were prepared by direct 3D printing from a polymer/drug blend. An investigation of the mechanical properties of 3D-printed scaffolds containing 0.5–5 wt% ciprofloxacin (CIP) or dexamethasone (DEX) showed almost no effect of the drug (compression modulus ~70–90 MPa) compared to unfilled PCL (74 MPa). At the same time, introducing the drug and increasing its content in the PCL matrix contributed to a 1.8–6.8-fold decrease in the specific surface area of the scaffold, depending on composition. The release of CIP and DEX in phosphate buffer solution and in the same buffer containing lipase revealed a faster release in enzyme-containing medium within 45 days. Furthermore, drug release was more intensive from scaffolds with a low drug load. Analysis of the release profiles using a number of mathematical dissolution models led to the conclusion that diffusion dominates over other probable factors. In vitro biological evaluation of the scaffolds containing DEX showed moderate toxicity against osteoblast-like and leukemia monocytic cells. Being 3D-printed together with PCL both drugs retain their biological activity. PCL/CIP and PCL/DEX scaffolds demonstrated antibacterial properties against Pseudomonas aeruginosa (a total inhibition after 48 h) and anti-inflammatory activity in experiments on TNFα-activated monocyte cells (a 4-time reduction in CD-54 expression relative to control), respectively. Full article
(This article belongs to the Special Issue 3D Printing of Polymer Materials: Recent Advances and Future Perspectives)
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21 pages, 7372 KiB  
Article
Study on the Equation of State and Jet Forming of 3D-Printed PLA and PLA-Cu Materials
by Jianya Yi, Ruijie Hao, Qing Ji, Siman Guan, Zhijun Wang and Jianping Yin
Polymers 2023, 15(17), 3564; https://doi.org/10.3390/polym15173564 - 28 Aug 2023
Viewed by 842
Abstract
In order to improve the research and development efficiency and quality of low-density liners in production and scientific research development, PLA and PLA-Cu composite liners were prepared based on 3D-printing technology. In this paper, the relationship between the shock wave velocity D and [...] Read more.
In order to improve the research and development efficiency and quality of low-density liners in production and scientific research development, PLA and PLA-Cu composite liners were prepared based on 3D-printing technology. In this paper, the relationship between the shock wave velocity D and the particle velocity u of PLA and PLA-Cu materials was tested by a one-stage light gas gun experiment device, and then the Grüneisen equation of state parameters of the two materials was obtained by fitting. The forming process of the two jets was numerically simulated by using the equation of state. When combined with the pulsed X-ray shooting results of the jets, it was found that the jets of the two materials showed obvious characteristics of “expansion particle flow”, and the head of the PLA jet had a gasification phenomenon. The length of the PLA jet at 20 μs in the numerical simulation was 127.2 mm, and the average length of the PLA jet at 20 μs in the pulsed X-ray shooting experiment was 100.45 mm. The length of the PLA jet gasification part accounted for about 21% of the total length of the jet. The average velocity of the head of the PLA jet is 7798.35 m/s, and the average velocity of the head of the PLA-Cu jet is 8104.25 m/s. In this paper, 3D-printing technology is used to prepare the liner for the first time, aiming to open up a new preparation technology and provide a new material selection for low-density material liners. Full article
(This article belongs to the Special Issue 3D Printing of Polymer Materials: Recent Advances and Future Perspectives)
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16 pages, 2508 KiB  
Article
Three-Dimensional Printed Shape Memory Gels Based on a Structured Disperse System with Hydrophobic Cellulose Nanofibers
by Angelina P. Prosvirnina, Alexander N. Bugrov, Natalya V. Bobrova, Eugene V. Sivtsov, Alexandra L. Nikolaeva, Almaz M. Kamalov, Maria P. Sokolova and Michael A. Smirnov
Polymers 2023, 15(17), 3547; https://doi.org/10.3390/polym15173547 - 26 Aug 2023
Cited by 1 | Viewed by 910
Abstract
Inks for 3D printing were prepared by dispersing bacterial cellulose nanofibers (CNF) functionalized with methacrylate groups in a polymerizable deep eutectic solvent (DES) based on choline chloride and acrylic acid with water as a cosolvent. After 3D printing and UV-curing, the double-network composite [...] Read more.
Inks for 3D printing were prepared by dispersing bacterial cellulose nanofibers (CNF) functionalized with methacrylate groups in a polymerizable deep eutectic solvent (DES) based on choline chloride and acrylic acid with water as a cosolvent. After 3D printing and UV-curing, the double-network composite gel consisting of chemically and physically crosslinked structures composed from sub-networks of modified CNF and polymerized DES, respectively, was formed. The rheological properties of inks, as well as mechanical and shape memory properties of the 3D-printed gels, were investigated in dynamic and static modes. It was shown that the optimal amount of water allows improvement of the mechanical properties of the composite gel due to the formation of closer contacts between the modified CNF. The addition of 12 wt% water results in an increase in strength and ultimate elongation to 11.9 MPa and 300%, respectively, in comparison with 5.5 MPa and 100% for an anhydrous system. At the same time, the best shape memory properties were found for an anhydrous system: shape fixation and recovery coefficients were 80.0 and 95.8%, respectively. Full article
(This article belongs to the Special Issue 3D Printing of Polymer Materials: Recent Advances and Future Perspectives)
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