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17 pages, 4693 KiB  
Article
Rheological Characterization and Printability of Sodium Alginate–Gelatin Hydrogel for 3D Cultures and Bioprinting
by Mohan Kumar Dey and Ram V. Devireddy
Biomimetics 2025, 10(1), 28; https://doi.org/10.3390/biomimetics10010028 (registering DOI) - 4 Jan 2025
Abstract
The development of biocompatible hydrogels for 3D bioprinting is essential for creating functional tissue models and advancing preclinical drug testing. This study investigates the formulation, printability, mechanical properties, and biocompatibility of a novel Alg-Gel hydrogel blend (alginate and gelatin) for use in extrusion-based [...] Read more.
The development of biocompatible hydrogels for 3D bioprinting is essential for creating functional tissue models and advancing preclinical drug testing. This study investigates the formulation, printability, mechanical properties, and biocompatibility of a novel Alg-Gel hydrogel blend (alginate and gelatin) for use in extrusion-based 3D bioprinting. A range of hydrogel compositions were evaluated for their rheological behavior, including shear-thinning properties, storage modulus, and compressive modulus, which are crucial for maintaining structural integrity during printing and supporting cell viability. The printability assessment of the 7% alginate–8% gelatin hydrogel demonstrated that the 27T tapered needle achieved the highest normalized Printability Index (POInormalized = 1), offering the narrowest strand width (0.56 ± 0.02 mm) and the highest printing accuracy (97.2%) at the lowest printing pressure (30 psi). In contrast, the 30R needle, with the smallest inner diameter (0.152 mm) and highest printing pressure (80 psi), resulted in the widest strand width (0.70 ± 0.01 mm) and the lowest accuracy (88.8%), resulting in a POInormalized of 0.274. The 30T and 27R needles demonstrated moderate performance, with POInormalized values of 0.758 and 0.558, respectively. The optimized 7% alginate and 8% gelatin blend demonstrated favorable printability, mechanical strength, and cell compatibility with MDA-MB-213 breast cancer cells, exhibiting high cell proliferation rates and minimal cytotoxicity over a 2-week culture period. This formulation offers a balanced approach, providing sufficient viscosity for precision printing while minimizing shear stress to preserve cell health. This work lays the groundwork for future advancements in bioprinted cancer models, contributing to the development of more effective tools for drug screening and personalized medicine. Full article
(This article belongs to the Section Biomimetic Design, Constructions and Devices)
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<p>(<b>a</b>) Scaffold grid design with extruded square along the path line and (<b>b</b>) layered scaffold configuration with 90° rotation and z-axis duplication.</p>
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<p>(<b>a</b>) Laser-cut square-shaped molds and (<b>b</b>) casting process for Alg-Gel hydrogel samples.</p>
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<p>MDA-MB-231 cells seeded on 3D-bioprinted scaffolds in a 12-well plate.</p>
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<p>Rheological characterization of hydrogel mixtures with varying alginate and gelatin concentrations (4% Alg–8% Gel, 5% Alg–6% Gel, 5% Alg–6% Gel, 7% Alg–8% Gel). (<b>a</b>) Storage modulus (G′) and loss modulus (G″) as a function of angular frequency, showing an increase in both moduli with higher alginate concentration; (<b>b</b>) tan δ vs. angular frequency for the hydrogel mixtures, with tan δ values consistently below 1 across all formulations; (<b>c</b>) shear viscosity as a function of shear rate, demonstrating shear-thinning behavior in all hydrogel mixtures. (<b>d</b>) Axial stress vs. compression percentage, highlighting distinct mechanical behaviors across formulations, with 4% Alg–8% Gel showing the highest compressive strength.</p>
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<p>Swelling ratio of Alg-Gel hydrogels over time.</p>
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<p>UATR spectra of (<b>a</b>) alginate, (<b>b</b>) alginate–gelatin, and (<b>c</b>) alginate–gelatin–calcium chloride.</p>
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<p>Three-dimensional bioprinting scaffold on Petri dish.</p>
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<p>Evaluation of cell proliferation and viability of MDA-MB-213 cells cultured on Alg-Gel hydrogels over two weeks: (<b>a</b>) cell viability at 1 day; (<b>b</b>) cell viability at 1 week; (<b>c</b>) cell viability at 2 weeks, confirming hydrogel cytocompatibility and support for long-term culture; (<b>d</b>) cell viability.</p>
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16 pages, 13175 KiB  
Article
An Open-Source 3D Printed Three-Fingered Robotic Gripper for Adaptable and Effective Grasping
by Francisco Yumbla, Emiliano Quinones Yumbla, Erick Mendoza, Cristobal Lara, Javier Pagalo, Efraín Terán, Redhwan Algabri, Myeongyun Doh, Tuan Luong and Hyungpil Moon
Biomimetics 2025, 10(1), 26; https://doi.org/10.3390/biomimetics10010026 (registering DOI) - 4 Jan 2025
Abstract
This research focuses on the design of a three-finger adaptive gripper using additive manufacturing and electromechanical actuators, with the purpose of providing a low-cost, efficient, and reliable solution for easy integration with any robot arm for industrial and research purposes. During the development [...] Read more.
This research focuses on the design of a three-finger adaptive gripper using additive manufacturing and electromechanical actuators, with the purpose of providing a low-cost, efficient, and reliable solution for easy integration with any robot arm for industrial and research purposes. During the development phase, 3D printing materials were employed in the gripper’s design, with Polylactic Acid (PLA) filament used for the rigid mechanical components and Thermoplastic Polyurethane (TPU) for the flexible membranes that distribute pressure to the resistive force sensors. Stress analysis and simulations were conducted to evaluate the performance of the components under load and to gradually refine the design of the adaptive gripper. It was ensured that the mechanism could integrate effectively with the robotic arm and be precisely controlled through a PID controller. Furthermore, the availability of spare parts in the local market was considered essential to guarantee easy and cost-effective maintenance. Tests were conducted on an actual robotic arm, and the designed gripper was able to effectively grasp objects such as a soda can and a pencil. The results demonstrated that the adaptive gripper successfully achieved various types of grasping, offering a scalable and economical solution that represents a significant contribution to the field of robotic manipulation in industrial applications. Full article
13 pages, 3107 KiB  
Article
Maxillectomy Guided by 3D Printing Versus Conventional Surgery for Patients with Head and Neck Cancer
by Sung Yool Park, Sung Ha Jung, Anna Seo, Hakjong Noh, Hwansun Lee, Hyo Jun Kim, Younghac Kim, Man Ki Chung, Han-Sin Jeong, Chung-Hwan Baek, Young-Ik Son and Nayeon Choi
Cancers 2025, 17(1), 140; https://doi.org/10.3390/cancers17010140 (registering DOI) - 4 Jan 2025
Viewed by 141
Abstract
Background: This study evaluates the impact of three-dimensional (3D) printing-guided maxillectomy compared with conventional maxillectomy on surgical precision and oncological outcomes in patients with head and neck cancer. Materials and Methods: A retrospective analysis was conducted on 42 patients undergoing maxillectomy (16 in [...] Read more.
Background: This study evaluates the impact of three-dimensional (3D) printing-guided maxillectomy compared with conventional maxillectomy on surgical precision and oncological outcomes in patients with head and neck cancer. Materials and Methods: A retrospective analysis was conducted on 42 patients undergoing maxillectomy (16 in a 3D printing-guided group and 26 in a conventional group). Patient demographics, tumor characteristics, and outcomes were compared. Survival outcomes were analyzed using the Kaplan–Meier method. Results: The 3D printing group showed higher rates of negative resection margins (81.3% vs. 76.9%) compared with the conventional group and a trend toward improved 5-year local recurrence-free survival (87.5% vs. 58.7%, respectively) and overall survival (84.4% vs. 70.1%, respectively). However, the differences were not statistically significant. Conclusions: Maxillectomy guided by 3D printing may offer enhanced surgical precision and improved local control in patients undergoing head and neck cancer surgeries. Further research with larger cohorts is necessary to confirm these findings. Full article
(This article belongs to the Special Issue Advancements in Head and Neck Cancer Surgery)
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<p>Example of 3D printing guidance design using Reconeasy-3D Software. (<b>A</b>) Preoperative virtual simulation created using DICOM data extracted from computed tomography (CT) and magnetic resonance imaging (MRI), virtually marking the areas for osteotomy guidance (<b>B</b>) The rapid prototype 3D model of the maxilla, displaying osteotomy lines to guide tumor resection and a prefabricated orbital mesh plate customized for the orbital floor defect, prepared for precise anatomical restoration during surgery. (<b>C</b>) Intraoperative view showing maxillectomy performed according to the preoperative plan created with 3D printing.</p>
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<p>Clinical images of 79 years old male who had 3D printing-guided salvage maxillectomy after the failure of definitive chemoradiation. (<b>A</b>) PET-CT revealed maxillary sinus cancer in anterolateral wall of sinus. (<b>B</b>) Preoperative CT coronal image showed maxillary sinus cancer involving orbital inferior wall, inferolateral wall of maxillary sinus. (<b>C</b>) Postoperative CT image revealed well-reconstructed orbital plated and anterolateral thigh free flap at 3 months after the surgery. (<b>D</b>) Intraoperative image of maxillectomy defect and reconstruction with anterolateral thigh free flap and prefabricated orbital mesh plate. (<b>E</b>,<b>F</b>) Endoscopic image of hard palate and nasal cavity reconstructed by anterolateral free flap at 3 months post operation.</p>
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<p>Kaplan–Meier survival plot with log-rank test between the 3D printing-guided maxillectomy group and conventional maxillectomy group. (<b>A</b>) Local recurrence free survival (<span class="html-italic">p</span> = 0.236); (<b>B</b>) overall recurrence free survival (<span class="html-italic">p</span> = 0.233); (<b>C</b>) overall survival (<span class="html-italic">p</span> = 0.435).</p>
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11 pages, 5555 KiB  
Article
Proportional Condylectomy Using a Titanium 3D-Printed Cutting Guide in Patients with Condylar Hyperplasia
by Wenko Smolka, Carl-Peter Cornelius, Katharina Theresa Obermeier, Sven Otto and Paris Liokatis
Craniomaxillofac. Trauma Reconstr. 2025, 18(1), 7; https://doi.org/10.3390/cmtr18010007 - 3 Jan 2025
Viewed by 329
Abstract
Background: The purpose of the study was to describe proportional condylectomy in patients with condylar hyperplasia using a titanium 3D-printed ultrathin wire mesh cutting guide placed below the planned bone resection. Methods: Eight patients with condylar hyperplasia underwent proportional condylectomy using an ultrathin [...] Read more.
Background: The purpose of the study was to describe proportional condylectomy in patients with condylar hyperplasia using a titanium 3D-printed ultrathin wire mesh cutting guide placed below the planned bone resection. Methods: Eight patients with condylar hyperplasia underwent proportional condylectomy using an ultrathin titanium 3D-printed cutting guide placed below the planned bone resection. The placement of the guide was facilitated by the incorporation of anatomical landmarks. The accuracy of bone resections guided by such devices was evaluated on postoperative radiographs. The mean postoperative follow-up was 30 months. Results: Surgery could be performed in all patients in the same manner as virtually planned. The fitting accuracy of the cutting guides was judged as good. Postoperative radiographs revealed that the virtually planned shape of the newly formed condylar head after condylectomy could be achieved. Conclusions: In conclusion, the use of virtual computer-assisted planning and CAD/CAM-based cutting guides for proportional condylectomy in unilateral condylar hyperplasia of the mandible offers high accuracy and guarantees very predictable results. Full article
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<p>Computer-assisted virtual planning of a proportional condylectomy of the right mandibular condyle. The original entire mandible with the distorted right condylar head is shown in purple. The healthy left hemi-mandible in yellow color has been horizontally mirrored and superimposed on the affected side to indicate the amount of resection needed to equal healthy conditions.</p>
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<p>(<b>a</b>) Virtual planning of a standalone cutting guide in lateral view (<b>b</b>) and frontal view. The portion of bone that is aimed to be resected is marked in red.</p>
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<p>Paired cutting guides for a combined stepwise proportional condylectomy procedure: (<b>a</b>) initial cutting guide to resect the cranial portion of the condylar head; (<b>b</b>) second cutting guide for resection of the lateral portion of the condylar head. Both guides have a plate hole for screw fixation in a coinciding bony drill hole.</p>
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<p>Patient with right CH and ipsilateral open bite. (<b>a</b>) Preoperative frontal view, (<b>b</b>) occlusion, and (<b>c</b>) panoramic X-ray. (<b>d</b>) Virtual planning preoperative frontal and lateral view. (<b>e</b>) Virtual planned cutting guide. (<b>f</b>) Virtual planned postoperative frontal and lateral view. (<b>g</b>) Intraoperative view with cutting guide. (<b>h</b>) Resected bone. (<b>i</b>) Intraoperative MMF. (<b>j</b>) Coronal plane of postoperative CT scan. (<b>k</b>) Postoperative occlusion. (<b>l</b>) Postoperative frontal view.</p>
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<p>Patient with right CH and ipsilateral open bite. (<b>a</b>) Preoperative frontal view, (<b>b</b>) occlusion, and (<b>c</b>) panoramic X-ray. (<b>d</b>) Virtual planning preoperative frontal and lateral view. (<b>e</b>) Virtual planned cutting guide. (<b>f</b>) Virtual planned postoperative frontal and lateral view. (<b>g</b>) Intraoperative view with cutting guide. (<b>h</b>) Resected bone. (<b>i</b>) Intraoperative MMF. (<b>j</b>) Coronal plane of postoperative CT scan. (<b>k</b>) Postoperative occlusion. (<b>l</b>) Postoperative frontal view.</p>
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<p>Patient with left CH and maxillary compensation with canting of the maxilla and downward deviation of the occlusal plane to the ipsilateral side. (<b>a</b>) Preoperative frontal view, (<b>b</b>) occlusion, and (<b>c</b>) panoramic X-ray. (<b>d</b>) Virtual planned cutting guide. (<b>e</b>) Virtual planned orthognatic surgery—Le Fort I Osteotomy. (<b>f</b>) Virtual planned postoperative frontal view. (<b>g</b>) Intraoperative view with cutting guide for condylectomie. (<b>h</b>). Resected bone. (<b>i</b>) Postoperative panoramic X-ray. (<b>j</b>) Postoperative occlusion. (<b>k</b>) Postoperative frontal view.</p>
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<p>Patient with left CH and maxillary compensation with canting of the maxilla and downward deviation of the occlusal plane to the ipsilateral side. (<b>a</b>) Preoperative frontal view, (<b>b</b>) occlusion, and (<b>c</b>) panoramic X-ray. (<b>d</b>) Virtual planned cutting guide. (<b>e</b>) Virtual planned orthognatic surgery—Le Fort I Osteotomy. (<b>f</b>) Virtual planned postoperative frontal view. (<b>g</b>) Intraoperative view with cutting guide for condylectomie. (<b>h</b>). Resected bone. (<b>i</b>) Postoperative panoramic X-ray. (<b>j</b>) Postoperative occlusion. (<b>k</b>) Postoperative frontal view.</p>
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10 pages, 861 KiB  
Article
Can Viewing Modality Affect Frontal Mandibular Bone Height Measurement? A Comparison Between 3D Digital Imaging and Communications in Medicine Viewer and Printed Portable Document Format Cone Beam Computer Tomography Reports
by Michael Solomonov, Yoav Shapinko, Ella Lalum, Joe Ben Itzhak, Sapir Argaman, Matan Schottig, Amit Halpern, Nirit Yavnai and Idan Stiklaru
Dent. J. 2025, 13(1), 22; https://doi.org/10.3390/dj13010022 - 3 Jan 2025
Viewed by 362
Abstract
Objectives: Buccal cortical bone dimensions are crucial in dental radiology, as they impact orthodontic treatment outcomes. Changes in alveolar bone dimensions can result in malocclusion and require interdisciplinary approaches for correction. The accurate quantification of buccal bone dimensions is crucial for appropriate treatment [...] Read more.
Objectives: Buccal cortical bone dimensions are crucial in dental radiology, as they impact orthodontic treatment outcomes. Changes in alveolar bone dimensions can result in malocclusion and require interdisciplinary approaches for correction. The accurate quantification of buccal bone dimensions is crucial for appropriate treatment planning and avoiding medico-legal issues. This study aimed to compare buccal bone height measurements between three-dimensional (3D) digital imaging and communications in medicine (DICOM) data and portable document format (PDF) cone beam computer topography reports for mandibular frontal teeth, testing the hypothesis of no difference in values between the two modalities. Methods: Each of the five observers performed a total of 720 height measurements (360 by DICOM and 360 by PDF), yielding a total of 3600 measurements overall. Results: Compared with the DICOM format, using PDF files was associated with a significantly greater rate of inability to carry out the measurements (8.8% vs. 3%, respectively, p < 0.001, chi-square). The average buccal bone height measured in the DICOM was 11.51 mm, which was significantly greater than the 10.35 mm measured in the PDF (p < 0.001). The mean height measured by the DICOM was consistently greater than that measured by the PDF, with highly significant differences in the findings of four of the examiners (p < 0.001). Conclusions: Viewing modality significantly affected the height of the buccal bone in the frontal mandibular area. Compared with the generated PDF reports, the 3D DICOM viewer performed better than the printed PDF and enabled more measurements in the target area. Full article
(This article belongs to the Special Issue Updates on Endodontics)
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<p>The buccal bone heights in the 3D DICOM and the PDF are similar.</p>
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<p>Compared with that in the PDF, the height of the buccal bone in the 3D DICOM is much greater.</p>
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10 pages, 535 KiB  
Article
Next-Generation Dental Materials: Exploring Bacterial Biofilm Formation on 3D-Printable Resin-Based Composites
by Emerson Koji Uehara, Gustavo Castro de Lima, Janaina de Cassia Orlandi Sardi, Luciene Cristina de Figueiredo, Jamil Awad Shibli, Thabet Asbi, Doron Haim and José Augusto Rodrigues
J. Funct. Biomater. 2025, 16(1), 12; https://doi.org/10.3390/jfb16010012 - 3 Jan 2025
Viewed by 215
Abstract
This study evaluated the microbial growth profile of subgingival multispecies biofilm on 3D-printable resin-based composites (PRBCs). A 96-well cell plate cultivated a 39-species biofilm associated with periodontitis over 7 days. Cylindrical specimens with 12 mm high and 3 mm diameters were prepared by [...] Read more.
This study evaluated the microbial growth profile of subgingival multispecies biofilm on 3D-printable resin-based composites (PRBCs). A 96-well cell plate cultivated a 39-species biofilm associated with periodontitis over 7 days. Cylindrical specimens with 12 mm high and 3 mm diameters were prepared by the PRBC group (Cosmos Temp-Yller; Prizma 3D Bio Crown; Prizma 3D Bio Prov) and an acrylic resin as control. Further, these specimens were immersed in the well plate to allow biofilm formation. After growing for 7 days, the metabolic biofilm activity was evaluated by colorimetric assay and the microbial profile by DNA-DNA hybridization. Kruskal–Wallis and Mann–Whitney tests evaluated each bacteria count and complex group. A greater biofilm formation was observed on PRBC groups than on acrylic resin. The microbiological profile of PRBC was associated with a less pathogenic biofilm, with an absence of a red complex. Acrylic resin showed low biofilm growth, but the biofilm profile was related to periodontal disease, characterized by red-complex bacteria. The selection of PRBC may contribute more effectively to maintaining periodontal health than acrylic resin. Full article
(This article belongs to the Special Issue Feature Papers in Dental Biomaterials (2nd Edition))
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<p>Pie charts describing the total counts of microbial complexes (×10<sup>5</sup>) and percentage detected by Checkerboard DNA-DNA hybridization. The size of the pie charts represents the proportion of total bacterial counts.</p>
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15 pages, 4340 KiB  
Article
Prototype of Self-Service Electronic Stethoscope to Be Used by Patients During Online Medical Consultations
by Iwona Chuchnowska and Katarzyna Białas
Sensors 2025, 25(1), 226; https://doi.org/10.3390/s25010226 - 3 Jan 2025
Viewed by 232
Abstract
This article presents the authors’ design of an electronic stethoscope intended for use during online medical consultations for patient auscultation. The goal of the project was to design an instrument that is durable, user-friendly, and affordable. Existing electronic components were used to create [...] Read more.
This article presents the authors’ design of an electronic stethoscope intended for use during online medical consultations for patient auscultation. The goal of the project was to design an instrument that is durable, user-friendly, and affordable. Existing electronic components were used to create the device and a traditional single-sided chest piece. Three-dimensional printing technology was employed to manufacture the prototype. Following the selection of the material, a static tensile strength test was conducted on the printed samples as part of the pre-implementation investigations. Results: Tests on samples made of PLA with a 50% hexagonal infill demonstrated a tensile strength of 36 MPa and an elongation of 4–5%, which was deemed satisfactory for the intended application in the stethoscope’s manufacture. The designed and manufactured electronic stethoscope presented in the article can be connected to headphones or speakers, enabling remote medical consultation. According to the opinion of doctors who tested it, it provides the appropriate sound quality for auscultation. This stethoscope facilitates the rapid detection and recognition of cardiac and respiratory activity in humans. Full article
(This article belongs to the Special Issue Non-Intrusive Sensors for Human Activity Detection and Recognition)
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<p>The CAD model of the fragment of the stethoscope housing with the main board fastening designed with Autodesk Inventor 2020.</p>
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<p>CAD model of stethoscope assembly designed with Autodesk Inventor 2020.</p>
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<p>Electronic remote stethoscope (controlling side).</p>
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<p>Electronic remote stethoscope (auscultation side).</p>
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<p>Tele-advice.</p>
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<p>An examination using a stethoscope.</p>
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<p>The spectrogram of a healthy lung.</p>
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<p>A spectrogram showing pathological changes during the auscultation of the lungs.</p>
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<p>The spectrogram of the heartbeat.</p>
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14 pages, 1654 KiB  
Article
Effect of Geometry on the Dissolution Behaviour of Complex Additively Manufactured Tablets
by Seyedebrahim Afkhami, Meisam Abdi and Reza Baserinia
J. Manuf. Mater. Process. 2025, 9(1), 11; https://doi.org/10.3390/jmmp9010011 - 3 Jan 2025
Viewed by 258
Abstract
Additive manufacturing (AM) processes, such as fused deposition modelling (FDM), have emerged as transformative technologies in pharmaceutical manufacturing, enabling the production of drug delivery systems with complex and customised geometries. These advancements provide precise control over drug release profiles and facilitate the development [...] Read more.
Additive manufacturing (AM) processes, such as fused deposition modelling (FDM), have emerged as transformative technologies in pharmaceutical manufacturing, enabling the production of drug delivery systems with complex and customised geometries. These advancements provide precise control over drug release profiles and facilitate the development of patient-specific medicines. This study investigates the dissolution behaviour of AM-fabricated tablets made from polyvinyl alcohol (PVA), a hydrophilic and biocompatible polymer widely used in drug delivery systems. The influence of the initial mass, surface area, and surface-area-to-volume ratio (S/V) on dissolution kinetics is evaluated for tablets with intricate geometries. Our findings demonstrate that these parameters, while critical for conventional tablet shapes, are insufficient to fully predict the dissolution behaviour of complex geometries. Furthermore, this study highlights how geometric modifications can enable the administration of the same drug dosage through sustained or immediate release profiles, offering enhanced versatility in drug delivery. By leveraging the geometric design freedom provided by AM technologies, this research underscores the potential for optimising drug delivery systems to improve therapeutic outcomes and patient compliance. Full article
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<p>Example isometric projections of the four geometries. From left to right: Solid Cylinder (SC), Hollow Cylinder 1 (HC1), Hollow Cylinder 2 (HC2), and Hollow Cylinder 3 (HC3).</p>
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<p>Example samples with similar surface areas. From left to right: Solid Cylinder (SC), Hollow Cylinder 1 (HC1), Hollow Cylinder 2 (HC2), and Hollow Cylinder 3 (HC3).</p>
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<p>(<b>a</b>) The calibration curve for converting the absorbance to the concentration of PVA dissolved in water (coefficient of determination, R<sup>2</sup> = 0.99), and (<b>b</b>) the UV absorption standard curve for the PVA.</p>
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<p>The changes in (<b>a</b>) average concentration and (<b>b</b>) percentage dissolved over time for samples with a similar mass. The error bars are generated using the standard deviation of the three repeat measurements.</p>
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<p>The changes in (<b>a</b>) average concentration and (<b>b</b>) percentage dissolved over time for samples with a similar surface area. The error bars are generated using the standard deviation of the three repeat measurements.</p>
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<p>The changes in (<b>a</b>) average concentration and (<b>b</b>) percentage dissolved over time for samples with a similar surface-area-to-volume ratio. The error bars are generated using the standard deviation of the three repeat measurements.</p>
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<p>Time to 50% dissolution for all studied specimens.</p>
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<p>Linear regression (LR) plots of cumulative drug release (% dissolved) versus the square root of time for specimens with a similar S/V fitted to the Higuchi model.</p>
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28 pages, 6406 KiB  
Review
Research Advancements in the Mechanical Performance and Functional Properties of Nanocomposites Reinforced with Surface-Modified Carbon Nanotubes: A Review
by Stefanos (Steve) Nitodas, Raj Shah and Mrinaleni Das
Appl. Sci. 2025, 15(1), 374; https://doi.org/10.3390/app15010374 - 2 Jan 2025
Viewed by 731
Abstract
This review summarizes the recent advancements in the mechanical properties of nanocomposites reinforced with surface-modified carbon nanotubes (CNTs). A range of matrices, namely, polymers, metals, and cement, is investigated, which have demonstrated increasing importance in a broad range of industrial sectors, such as [...] Read more.
This review summarizes the recent advancements in the mechanical properties of nanocomposites reinforced with surface-modified carbon nanotubes (CNTs). A range of matrices, namely, polymers, metals, and cement, is investigated, which have demonstrated increasing importance in a broad range of industrial sectors, such as 3D printing, automotive, construction, and coatings. The strengthening mechanisms that CNTs impart in composites are reviewed, and synergistic effects with their surface groups or co-additives are analyzed, including wettability, mechanical interlocking, and chemical bonding. Different mechanical and functional properties of the CNT-reinforced nanocomposites are analyzed, such as tensile strength, flexural strength, impact resistance, thermal conductivity, and electrical conductivity. The improvements in these properties for a variety of CNT-based composites are presented, and details on how these improvements were attained are discussed. The review concludes that surface modification of CNTs has proven to be of high importance, enhancing compatibility with various matrices and facilitating improvements in the nanocomposite properties. Suggestions for viable CNT-based composites for use in the studied applications are also provided. Full article
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<p>Possible wrappings of the two-dimensional graphene sheet into tubular forms. The red dots represent metallic (metal, conductive) CNTs and the black dots represent semiconductive CNTs [<a href="#B38-applsci-15-00374" class="html-bibr">38</a>].</p>
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<p>Multi-walled CNTs (MWCNTs) [<a href="#B51-applsci-15-00374" class="html-bibr">51</a>].</p>
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<p>Ashby plot of Young’s modulus vs. tensile strength that compares the mechanical properties of conventional polymer composites, including glass fiber-reinforced plastic (GFRP) and carbon fiber-reinforced plastic (CFRP), with CNTs or graphene-based polymer composites [<a href="#B67-applsci-15-00374" class="html-bibr">67</a>].</p>
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<p>Electrical conductivity of PP composites as a function of CNTs weight fraction [<a href="#B68-applsci-15-00374" class="html-bibr">68</a>].</p>
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<p>Flexural, tensile, and compressive properties of CNT/PP composites at 1.0 wt% CNT loading [<a href="#B68-applsci-15-00374" class="html-bibr">68</a>].</p>
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<p>SEM images showing the dispersion states of different fillers in PVDF composites with the same content of 10 wt%. (<b>a</b>) Pure PVDF, (<b>b</b>) MWCNTs/PVDF, (<b>c</b>) GE/PVDF, (<b>d</b>) p-MWCNTs/GE/PVDF, (<b>e</b>) a-MWCNTs/GE/PVDF, and (<b>f</b>) s-MWCNTs/GE/PVDF) [<a href="#B79-applsci-15-00374" class="html-bibr">79</a>].</p>
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<p>(<b>a</b>) Thermal conductivity of PVDF composites with GE, p-MWCNTs, and p-MWCNTs/GE. (<b>b</b>) Thermal conductivity of PVDF composites with different contents of s-MWCNTs/GE, a-MWCNTs/GE, and p-MWCNTs/GE [<a href="#B79-applsci-15-00374" class="html-bibr">79</a>].</p>
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<p>Schematic diagram of the preparation of MIPs and CNT-MIPs/PPS [<a href="#B85-applsci-15-00374" class="html-bibr">85</a>].</p>
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<p>Friction coefficient (<b>a</b>) and wear rate (<b>b</b>) of CNTs/PPS composites as a function of CNT content [<a href="#B85-applsci-15-00374" class="html-bibr">85</a>].</p>
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<p>(<b>a</b>) Schematic diagram of the fabrication of chemically modified multi-wall carbon nanotubes (H-CNTs); (<b>b</b>) Schematic diagram of the fabrication of PEGylated inorganic fullerene tungsten sulfide (P-IF-WS2) nanofillers; (<b>c</b>) laser sintered PA12/H-CNT/P-IF-WS2 nanocomposites [<a href="#B88-applsci-15-00374" class="html-bibr">88</a>].</p>
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<p>Vickers hardness and density for the samples: AlCTS01: 100% Al (aluminum); AlCTS02: 99 wt% Al + 0.5 wt% CNT + 0.5 wt% TiC; AlCTS03: 98.5 wt% Al + 0.5 wt% CNT + 1 wt% TiC; AlCTS04: 98 wt% Al + 0.5 wt% CNT + 1.5 wt% TiC; and AlCTS05 97.5 wt% Al + 0.5 wt% CNT + 2 wt% TiC) [<a href="#B113-applsci-15-00374" class="html-bibr">113</a>].</p>
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<p>Results of shear strength for AlCoFeMnNi and AlCoFeMnNi-1 wt% CNT nanocomposite samples sintered at (<b>a</b>) 850 and (<b>b</b>) 950 °C [<a href="#B115-applsci-15-00374" class="html-bibr">115</a>].</p>
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<p>Integral peak area ratio (A) for CH and C3S as a function of MWCNT content (%) in cement composites [<a href="#B124-applsci-15-00374" class="html-bibr">124</a>].</p>
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<p>Three-dimensional surface plots and 2D contour plots showing the influence of two process variables on compressive strength, while the third process variable is fixed: (<b>a</b>) Surfactant (S) is fixed at 0.012 wt%; (<b>b</b>) Titania (T) is fixed at 1.0 wt%; and (<b>c</b>) MWCNTs (C) are fixed at 0.06 wt% [<a href="#B125-applsci-15-00374" class="html-bibr">125</a>].</p>
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<p>Flexural strength (<b>a</b>) and compressive strength (<b>b</b>) of CNT-based cement composites [<a href="#B126-applsci-15-00374" class="html-bibr">126</a>]. The red line has been drawn to indicate the level of the reference sample in order to demonstrate further the improvements observed in the CNTs samples.</p>
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<p>SEM images: (<b>a</b>) Reference sample; (<b>b</b>) p-CNT10 sample; (<b>c</b>) c-CNT10 sample; (<b>d</b>) m-CNT10 sample; and (<b>e</b>,<b>f</b>) m-CNT20 sample [<a href="#B126-applsci-15-00374" class="html-bibr">126</a>].</p>
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17 pages, 4058 KiB  
Article
A Dynamic Tensile Method Using a Modified M-Typed Specimen Loaded by Split Hopkinson Pressure Bar
by Yuan Lin, Jitang Fan, Xinlu Yu, Yingqian Fu, Gangyi Zhou, Xu Wang and Xinlong Dong
Materials 2025, 18(1), 149; https://doi.org/10.3390/ma18010149 - 2 Jan 2025
Viewed by 216
Abstract
Obtaining reliable dynamic mechanical properties through experiments is essential for developing and validating constitutive models in material selection and structural design. This study introduces a dynamic tensile method using a modified M-type specimen loaded by a split Hopkinson pressure bar (SHPB). A closed [...] Read more.
Obtaining reliable dynamic mechanical properties through experiments is essential for developing and validating constitutive models in material selection and structural design. This study introduces a dynamic tensile method using a modified M-type specimen loaded by a split Hopkinson pressure bar (SHPB). A closed M-type specimen was thus employed. Finite element simulations and experiments were used to validate the design of the M-type specimen, which was fabricated using 17-4PH (precipitation hardening) stainless steel powder with a 3D (three-dimensional) selected laser melting (SLM) printer. After verifying force balance and uniform deformation in the tensile region, tensile tests were conducted across strain rates from quasi-static to a strain rate of 5900 s−1. The results demonstrated that this method effectively assessed the dynamic tensile behaviors of stainless steel at high strain rates, and achieved both ultra-high strain rates and large plastic deformation. Full article
(This article belongs to the Special Issue 3D & 4D Printing in Engineering Applications, 2nd Edition)
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<p>Schematic diagram of the 3D-printed building process: (<b>a</b>) EOS M280 3D printer, (<b>b</b>) schematic diagram of laser scanning, (<b>c</b>) laser beam, (<b>d</b>) M-type specimen, and (<b>e</b>) build process of specimen.</p>
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<p>The loading mechanism of the M-type specimen: (<b>a</b>) SHPB loading devices, (<b>b</b>) tensile gauge of DE and D<sub>1</sub>E<sub>1</sub> in M-type specimen in (<b>a</b>), (<b>c</b>) detail of specimen, and (<b>d</b>) tensile gauge section of D<sub>1</sub>E<sub>1</sub> shown in the dash box of (<b>c</b>).</p>
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<p>The experimental loading and measuring setups: (<b>a</b>) experimental apparatus of SHPB, ultra-high-speed camera, and flash lights, (<b>b</b>) the image captured by camera, and (<b>c</b>) the principle of DIC method.</p>
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<p>A 3D finite element model was created in Abaqus/Explicit, including the bullet, incident bar, transmission bar, and specimen.</p>
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<p>The comparation of stress and deformation for opening M-type specimen and closed M-type specimen using FE simulation: (<b>a</b>) shape of opening M-type specimen, (<b>b</b>) shape of closed M-type specimen, (<b>c</b>) the stress distribution and deformation of opening M-type specimen, and (<b>d</b>) the stress distribution and deformation of closed M-type specimen.</p>
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<p>Evaluation of the response of the M-shaped specimen and the dynamic force balance at both ends: (<b>a</b>) the incident, reflected, and transmitted waves, (<b>b</b>) the force balance reached in SHPB test, (<b>c</b>) the evolution of force and deformation of specimen, and (<b>d</b>) the stress distribution was uniformed along the tensile gauge.</p>
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<p>The correction of mechanical response for the M-shaped specimen: (<b>a</b>) load–displacement curve of <span class="html-italic">F</span>(<span class="html-italic">t</span>)–<span class="html-italic">U</span>(<span class="html-italic">t</span>), (<b>b</b>) the plastic true stress–strain curve.</p>
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<p>The 3D-printed stainless steel specimen and the typical stress waves measured by SHPB: (<b>a</b>) the microstructure at the direction of cross-section; (<b>b</b>) the microstructure at the direction of longitudinal section; (<b>c</b>) the typical set of incident, reflected, and transmitted wave signals obtained by SHPB; and (<b>d</b>) the 3D-printed M-type specimen.</p>
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<p>The deformation and fracture sequence of the M-type specimen (<b>a1</b>–<b>a4</b>), the detail of tensile gauge section (<b>b1</b>–<b>b4</b>), and the evolution of tensile strain analyzed by DIC method (<b>c1</b>–<b>c3</b>). The corresponding stress and strain development are shown in (<b>d</b>).</p>
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<p>True stress–plastic strain curves of 3D-printed stainless steel obtained by M-type specimen method with different strain rates.</p>
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17 pages, 26057 KiB  
Article
Staggered Design of UV–Curable Polymer Microneedle Arrays with Increased Vertical Action Space
by Baoling Jia, Tiandong Xia, Yangtao Xu and Bei Li
Polymers 2025, 17(1), 104; https://doi.org/10.3390/polym17010104 - 2 Jan 2025
Viewed by 241
Abstract
Recent studies have identified microneedle (MN) arrays as promising alternatives for transdermal drug delivery. This study investigated the properties of novel staggered MN arrays design featuring two distinct heights of MNs. The staggered MN arrays were precisely fabricated via PμSL light-cured 3D printing [...] Read more.
Recent studies have identified microneedle (MN) arrays as promising alternatives for transdermal drug delivery. This study investigated the properties of novel staggered MN arrays design featuring two distinct heights of MNs. The staggered MN arrays were precisely fabricated via PμSL light-cured 3D printing technology. The arrays were systematically evaluated for their morphology, fracture force, skin penetration ability, penetration mechanism, and drug delivery capability. The results demonstrated that the staggered MN arrays punctured the skin incrementally, leveraging the benefits of skin deformation during the puncture process. This approach effectively reduced the puncture force needed, achieving a maximum reduction of approximately 80.27% due to variations in the staggered height. Additionally, the staggered design facilitated skin penetration, as confirmed by the results of the rat skin hematoxylin-eosin (H&E) staining experiments. Compared with 3D-printed planar structures and highly uniform MN arrays, the staggered design exhibited enhanced hydrophilicity, as evidenced by a reduction in the contact angle from approximately 93° to 70°. Simulated drug release images of both coated and hollow staggered MNs illustrated the release and delivery capabilities of these structures across various skin layers, and the staggered design expanded the effective area of the MN arrays within the vertical dimension of the skin layers. This study offers both experimental and theoretical foundations for developing MN arrays with three–dimensional structural distributions, thereby facilitating advancements in MN array technology. Full article
(This article belongs to the Special Issue Advanced Processing Strategy for Functional Polymer Materials)
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<p>Arrangement of the MNs in array patches: (<b>a</b>) #1 MN arrays with a height of 0.8 mm; (<b>b</b>) #2 MN arrays with heights of 0.8 mm and 0.96 mm; (<b>c</b>) #3 MN arrays with heights of 0.8 mm and 1.04 mm; and (<b>d</b>) #4 MN arrays with heights of 0.8 mm and 1.12 mm.</p>
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<p>Photographs of MN patches puncture rats: (<b>a</b>) #1 MN arrays; (<b>b</b>) #2 MN arrays; (<b>c</b>) #3 MN arrays; (<b>d</b>) # 4MN arrays.</p>
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<p>Schematic of the mechanical properties of the MN patches: (<b>a</b>) the fracture force, and (<b>b</b>) penetration force test on porcine skin.</p>
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<p>Morphology of the MN arrays: (<b>a</b>) digital microscope images and (<b>b</b>) SEM micrographs.</p>
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<p>Mechanical compression tests of MN arrays: (<b>a</b>) fracture force of MN arrays and (<b>b</b>) fracture force of individual MNs.</p>
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<p>Force diagram of MN arrays puncturing porcine skin: (<b>a</b>) penetration force curves of MN arrays; (<b>b</b>) penetration force of MN arrays; and (<b>c</b>) displacement curves of MN arrays.</p>
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<p>H&amp;E staining of the rat skin penetrated by MNs: (<b>a</b>) #1 MN arrays; (<b>b</b>) #2 MN arrays; (<b>c</b>) #3 MN arrays; and (<b>d</b>) #4 MN arrays. Graphical representation: The black dotted line indicates the puncture outline, and the red dotted line indicates the puncture depth.</p>
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<p>Puncture processes of staggered MN arrays: (<b>a</b>) physical pictures and (<b>b</b>) schematic diagrams.</p>
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<p>The hydrophilicity for MN arrays: (<b>a</b>) backing layer; (<b>b</b>) #1 MN arrays; (<b>c</b>) #2 MN arrays; (<b>d</b>) #3 MN arrays; (<b>e</b>) #4 MN arrays; and (<b>f</b>) contact angle of MN arrays.</p>
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<p>Drug release behavior of the coated MN arrays: (<b>a</b>) photographs of the rhodamine-B-coated MNs; (<b>b</b>) photographs of the released rhodamine B from the MN patches into the agarose gel; and (<b>c</b>) the color of the agarose gel containing released rhodamine B over time.</p>
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<p>Drug release behavior of the hollow MN arrays: (<b>a</b>) morphology of the hollow MN arrays; (<b>b</b>) physical picture of the hollow MN puncture into the agarose gel; and (<b>c</b>) the color of the agarose gel over time.</p>
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30 pages, 18127 KiB  
Article
Innovative Approaches to Material Selection and Testing in Additive Manufacturing
by Alexandr Fales, Vít Černohlávek, Jan Štěrba, Milan Dian and Marcin Suszyński
Materials 2025, 18(1), 144; https://doi.org/10.3390/ma18010144 - 2 Jan 2025
Viewed by 254
Abstract
This study focuses on selecting a suitable 3D printer and defining experimental methods to gather the necessary data for determining the optimal filament material for printing components of the VEX GO and VEX IQ robotic kits. The aim is to obtain the required [...] Read more.
This study focuses on selecting a suitable 3D printer and defining experimental methods to gather the necessary data for determining the optimal filament material for printing components of the VEX GO and VEX IQ robotic kits. The aim is to obtain the required data to identify an appropriate filament material and set 3D printing parameters to achieve the desired mechanical properties of the parts while maintaining cost-effectiveness. Another key objective is achieving optimal operational functionality, ensuring the required part performance with minimal printing costs. It is desirable for the modeled and printed parts to exhibit the required mechanical properties while maintaining economic efficiency. Another crucial aspect is achieving optimal functionality of the produced parts with minimal printing costs. This will be assessed by analyzing the impact of key 3D printing technology parameters, focusing in this research phase on material selection. The criteria for selecting filament materials include ease of printability under the conditions of primary and secondary schools, simplicity of printing, minimal need for post-processing, and adequate mechanical properties verified through experimental measurements and destructive tests on original parts from VEX GO and VEX IQ kits. The study analyzed various filaments regarding their mechanical properties, printability, and cost-effectiveness. The most significant practical contribution of this study is selecting a suitable filament material tested through a set of destructive tests, emphasizing maintaining the mechanical properties required for the real-life application of the parts. This includes repetitive assembly and disassembly of various robotic model constructions and their activation for demonstration purposes and applications of STEM/STEAM/STREAM methods in the educational process to achieve the properties of original components. Additionally, the study aims to set up 3D printing such that even a beginner-level operator, such as a primary or secondary school student under the supervision of their teacher or a teacher with minimal knowledge and experience in 3D printing, can successfully execute it. Further ongoing research focuses on evaluating the effects of characteristic 3D printing parameters, such as infill and perimeter, on the properties of 3D-printed parts through additional measurements and analyses. Full article
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<p>Printer Original Prusa MK4.</p>
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<p>Original part 2 × 8 Smooth Panel (228-2500-524) VEX—top side.</p>
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<p>Original part 2 × 8 Smooth Panel (228-2500-524) VEX—bottom side.</p>
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<p>Original part 2 × 12 Beam (228-2500-026) VEX—top side.</p>
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<p>Original part 2 × 12 Beam (228-2500-026) VEX—bottom side.</p>
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<p>Modified part 2 × 12 Beam (228-2500-026) VEX—top side.</p>
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<p>Modified part 2 × 12 Beam (228-2500-026) VEX—bottom side.</p>
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<p>Static tensile test—before and after the test completion.</p>
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<p>Tensile load test—multiple representations of the loading force curves—Original.</p>
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<p>Tensile load test—multiple representations of the loading force curves—PLA.</p>
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<p>Tensile load test—multiple representations of the loading force curves—PET-G1.</p>
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<p>Tensile load test—multiple representations of the loading force curves—PET-G2.</p>
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<p>Tensile load test—multiple representations of the loading force curves—ASA.</p>
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<p>Tensile load test—multiple representations of the loading force curves—ABS.</p>
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<p>Deflection test—before and after the test.</p>
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<p>Deflection test—multiple representations of the applied force curves—Original.</p>
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<p>Deflection test—multiple representations of the applied force curves—PLA.</p>
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<p>Deflection test—multiple representations of the applied force curves—PET-G1.</p>
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<p>Deflection test—multiple representations of the applied force curves—PET-G2.</p>
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<p>Deflection test—multiple representations of the applied force curves—ASA.</p>
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<p>Deflection test—multiple representations of the applied force curves—ABS.</p>
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13 pages, 9198 KiB  
Article
A PVA–Brookite Composite: The Effect of Plasma Pre-Treatment on the Thermal, Mechanical, and Photochromic Properties
by Anastasia Evdokimova, Valeriya Shibaeva, Nikolay Sirotkin, Anton Kraev, Anton Manakhov and Anna Khlyustova
J. Compos. Sci. 2025, 9(1), 7; https://doi.org/10.3390/jcs9010007 - 2 Jan 2025
Viewed by 463
Abstract
A composite material based on polyvinyl alcohol (PVA) and brookite-phase titanium dioxide (TiO2) was synthesized using a straightforward method that involved combining the polymer with a sol as a filler. The composites were analyzed using Fourier transform infrared (FTIR) spectroscopy, scanning [...] Read more.
A composite material based on polyvinyl alcohol (PVA) and brookite-phase titanium dioxide (TiO2) was synthesized using a straightforward method that involved combining the polymer with a sol as a filler. The composites were analyzed using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC), and mechanical testing. The effects of treating the sol with underwater discharge plasma utilizing different electrode materials on the surface morphology, mechanical properties, thermal stability, and optical (photochromic) characteristics of the composites were investigated. FTIR spectral analysis indicated the presence of a chemical bond between the polymer matrix and the filler particles, as evidenced by the appearance of new peaks in the region of 700–500 cm−1. Preliminary plasma treatment was shown to enhance the thermal stability, strength, and elasticity of the PVA-based composite. These improvements resulted from the modification of the filler (sol) due to plasma activity. The resulting composites exhibited a low photocolorization rate and a high bleaching rate. Such composites represent a promising material for use as inks in 3D printing. Full article
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<p>DSC analysis of samples.</p>
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<p>AFM images of samples 1 (<b>a</b>), 2 (<b>b</b>), 3 (<b>c</b>), 4 (<b>d</b>), and 5 (<b>e</b>).</p>
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<p>SEM images of sample 2 (<b>a</b>), sample 3 (<b>b</b>), sample 4 (<b>c</b>), and sample 5 (<b>d</b>).</p>
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<p>Mechanical properties of samples.</p>
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<p>Absorption spectra of composites after 15 min of light irradiation (<b>a</b>) and typical kinetic curves of photocoloration and bleaching of composites with TiO<sub>2</sub> structures (<b>b</b>).</p>
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<p>PVA and PVP’s cross-linking mechanism.</p>
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24 pages, 11240 KiB  
Article
Study of the Interplay Among Melt Morphology, Rheology and 3D Printability of Poly(Lactic Acid)/Poly(3-Hydroxybutyrate-Co-3-Hydroxyvalerate) Blends
by Marco Costantini, Flavio Cognini, Roberta Angelini, Sara Alfano, Marianna Villano, Andrea Martinelli, David Bolzonella, Marco Rossi and Andrea Barbetta
J. Funct. Biomater. 2025, 16(1), 9; https://doi.org/10.3390/jfb16010009 - 1 Jan 2025
Viewed by 447
Abstract
Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as [...] Read more.
Polymeric materials made from renewable sources that can biodegrade in the environment are attracting considerable attention as substitutes for petroleum-based polymers in many fields, including additive manufacturing and, in particular, Fused Deposition Modelling (FDM). Among the others, poly(hydroxyalkanoates) (PHAs) hold significant potential as candidates for FDM since they meet the sustainability and biodegradability standards mentioned above. However, the most utilised PHA, consisting of the poly(hydroxybutyrate) (PHB) homopolymer, has a high degree of crystallinity and low thermal stability near the melting point. As a result, its application in FDM has not yet attained mainstream adoption. Introducing a monomer with higher excluded volume, such as hydroxyvalerate, in the PHB primary structure, as in poly(hydroxybutyrate-co-valerate) (PHBV) copolymers, reduces the degree of crystallinity and the melting temperature, hence improving the PHA printability. Blending amorphous poly(lactic acid) (PLA) with PHBV enhances further PHA printability via FDM. In this work, we investigated the printability of two blends characterised by different PLA and PHBV weight ratios (25:75 and 50:50), revealing the close connection between blend microstructures, melt rheology and 3D printability. For instance, the relaxation time associated with die swelling upon extrusion determines the diameter of the extruded filament, while the viscoelastic properties the range of extrusion speed available. Through thoroughly screening printing parameters such as deposition speed, nozzle diameter, flow percentage and deposition platform temperature, we determined the optimal printing conditions for the two PLA/PHBV blends. It turned out that the blend with a 50:50 weight ratio could be printed faster and with higher accuracy. Such a conclusion was validated by replicating with remarkable fidelity high-complexity objects, such as a patient’s cancer-affected iliac crest model. Full article
(This article belongs to the Special Issue Advanced Technologies for Processing Functional Biomaterials)
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<p>DSC thermograms of neat PLA, PLA/PHBV50:50 and PLA/PHBV25:75 blends: (<b>A</b>) first heating; (<b>B</b>) cooling; and (<b>C</b>) second heating scans all carried out at 10 °C min<sup>−1</sup>.</p>
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<p>SEM micrographs of cryogenically fractured cross-sections of PLA/PHBV blends: (<b>a</b>) PLA/PHBV50:50; (<b>b</b>) PLA/PHBV25:75.</p>
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<p>Rheological measurements of PLA/PHBV50:50 and PLA/PHBV 25:75 blends: (<b>a</b>) the effect of shear rate and temperature on the shear viscosity; (<b>b</b>) complex viscosity versus frequency of oscillation, (<b>c</b>) storage (<span class="html-italic">G</span>′, empty symbols) and loss moduli (<span class="html-italic">G</span>″, filled symbols) and (<b>d</b>) loss factor (tan <span class="html-italic">δ</span>) versus angular frequency. (<b>e</b>) Cole–Cole plots of imaginary (<span class="html-italic">η</span>″) versus real viscosity (<span class="html-italic">η</span>′) (the dotted vertical line shows an example of the extrapolation from a curve maximum to the X axis for the determination of the relaxation time (<span class="html-italic">τ<sub>c</sub></span>)) and (<b>f</b>) of the storage modulus versus the loss modulus. (<b>g</b>) First normal stress (<span class="html-italic">N</span><sub>1</sub>) as a function of angular frequency (<span class="html-italic">ω</span>).</p>
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<p>Dependence of filament diameter on extrusion speed and nozzle diameter at 180 °C for PLA/PHBV 50:50 (<b>a</b>) and PLA/PHBV 25:75 (<b>b</b>), with (<b>c</b>) showing the overlap of graphs for comparison.</p>
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<p>Nominal dimensions of the printed specimens using the blend PLA/PHBV50:50. Dependence of samples dimension on % flux: (<b>a</b>) cube (10 × 10 × 10 mm<sup>3</sup>) and cylinder (d = 10 mm, h = 10 mm), (<b>b</b>) dumbbell (115 × 13 × 3 mm<sup>3</sup>). (<b>c</b>). Influence of initial layer flow rate % on dumbbell length and degree of warpage. The horizontal dotted lines mark the expected dimension according to the CAD models.</p>
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<p>Dependence of printed specimen dimension on % flow: (<b>a</b>) cube, (<b>b</b>) cylinder, (<b>c</b>) dumbbell, (<b>d</b>) influence of flow % of the first layer on dumbbell length. All specimens are obtained from PLA/PHBV50:50. The red dotted horizontal lines mark the expected dimension according to the CAD models.</p>
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<p>(<b>a</b>) Influence of specimen length (<span class="html-italic">L</span>) for two different number of layers and (<b>b</b>) specimen number of layers (<span class="html-italic">n</span>) for three different specimen lengths on warping (<span class="html-italic">θ</span>). Specimens were printed using the PLA/PHBV25:75blend. Deposition plate temperature: 25 °C; specimen width: 10 mm. On the right side of the plots, specimens’ photographs illustrate the influence of length and number of layers on warping angle. Photographs are not in scale.</p>
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<p>Degree of warping as a function of temperature for the two blends: PLA/PHBV27:75 and PLA/PHBV50:50. Specimens’ dimension: length: 50 mm, width: 10 mm, number of layers: 70. On the right, photographs of two lamellas characterised by different number of layer and printed at 50 and 90 °C are shown.</p>
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<p>A 3D CAD model of the shaft support (<b>a</b>), and of the model including the supporting structure (shown in blue) (<b>b</b>). (<b>c</b>) photos of the printed shaft support and (<b>d</b>) computed X-ray microtomography (μCT) 3D rendering of the printed model from lateral and frontal views.</p>
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<p>(<b>a</b>) 3D CAD model of the iliac crest with overhanging surfaces evidenced in red. (<b>b</b>) Supporting structures (shown in blue) for the overhanging parts from a lateral view and from the top show the square grid pattern. (<b>c</b>) Photographs of the printed model from two different views. (<b>d</b>) Computed X-ray microtomography (μCT) 3D rendering of the printed model from frontal and lateral views.</p>
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22 pages, 5069 KiB  
Article
3D Printed Ni–Cu Sodalite Catalysts for Sustainable γ-Valerolactone Production from Levulinic Acid—Effect of the Copper Content and the Method of Preparation
by Margarita Popova, Boian Mladenov, Ivan Dimitrov, Momtchil Dimitrov, Violeta Mitova, Yavor Mitrev, Daniela Kovacheva, Nikolay Velinov, Daniela Karashanova and Silviya Boycheva
Processes 2025, 13(1), 72; https://doi.org/10.3390/pr13010072 - 1 Jan 2025
Viewed by 614
Abstract
Coal fly ash zeolites with Sodalite structure were synthesized by ultrasound-assisted double stage fusion-hydrothermal synthesis. Monometallic Ni and bimetallic Ni–Cu supported catalysts with 5 wt.% Ni and different copper contents of 1.5, 2.5 and 5.0 wt.% Cu were prepared by post-synthesis incipient wetness [...] Read more.
Coal fly ash zeolites with Sodalite structure were synthesized by ultrasound-assisted double stage fusion-hydrothermal synthesis. Monometallic Ni and bimetallic Ni–Cu supported catalysts with 5 wt.% Ni and different copper contents of 1.5, 2.5 and 5.0 wt.% Cu were prepared by post-synthesis incipient wetness impregnation. The catalysts were characterized by X-ray powder diffraction, N2 physisorption, transmission electron microscopy (TEM), Mössbauer spectroscopy and H2 temperature programmed reduction analysis. It was found that crystalline Cu0 and NixCuy intermetallic nanoparticles were formed in the reduced powder and 3D printed catalysts and that they affected the reducibility of the catalytically active nickel phase. Three-dimensionally printed 5Ni2.5Cu/Sodalite catalysts were prepared via modification with metals before and after 3D printing for comparative studies. The powder and 3D printed catalysts were studied in the lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The formation of NiCu alloy, which is found on the powder and 3D printed catalysts, favors their catalytic performance in the studied reaction. In contrast with powder catalysts, the preservation of the Sodalite structure was detected for all 3D printed samples and was found to have a positive influence on the metal dispersion registered in the 3D spent catalysts. The powder 5Ni2.5Cu/Sodalite catalyst showed the highest LA conversion and high GVL yield at 150 °C reaction temperature. Three-dimensionally printed catalysts show more stable catalytic activity than powder catalysts due to the preservation of the zeolite structure and metal dispersion. Full article
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Graphical abstract

Graphical abstract
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<p>Three-dimensional catalytic element software modeling: 3D model design (<b>a</b>), geometric dimensions (<b>b</b>), creating sketch (<b>c</b>) and extruded element (<b>d</b>).</p>
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<p>G code creation of created 3D model design of the catalytic element: (<b>a</b>) imported 3D model in slicer; (<b>b</b>) G code imported to 3D printer.</p>
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<p>3D printing of catalytic elements from developed inks.</p>
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<p>XRPD patterns of the studied catalysts.</p>
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<p>N<sub>2</sub> physisorption isotherms (<b>a</b>) and pore size distributions (<b>b</b>) of the studied samples.</p>
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<p>TPR–TG profiles of the catalysts studied.</p>
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<p>Mössbauer spectra of the nickel- and copper-modified samples and the 550 °C reduced sample.</p>
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<p>XRPD patterns of the spent catalysts.</p>
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<p>Bright field TEM micrographs (<b>a</b>,<b>d</b>), the corresponding histograms of the nanoparticles size distribution, SAED patterns (<b>b</b>,<b>e</b>) and the HRTEM images (<b>c</b>,<b>f</b>) of the powder 5Ni2.5Cu/sodalite reduced (<b>a</b>–<b>c</b>) and spent (<b>d</b>–<b>f</b>) catalysts.</p>
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<p>Scheme for the preparation of the 3D printed catalysts used in LA hydrogenation to GVL.</p>
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<p>XRPD of the 3D printed spent catalysts.</p>
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<p>Bright field TEM micrographs (<b>a</b>,<b>d</b>,<b>g</b>,<b>j</b>), the corresponding histograms of the size distribution of the nanoparticles, SAED patterns (<b>b</b>,<b>e</b>,<b>h</b>,<b>k</b>) and the HRTEM images (<b>c</b>,<b>f</b>,<b>i</b>,<b>l</b>) of the 3D printed 5Ni2.5Cu/Sodalite catalysts, as follows: 3D1 reduced (<b>a</b>–<b>c</b>), 3D1 spent (<b>d</b>–<b>f</b>), 3D2 reduced (<b>g</b>–<b>i</b>) and 3D2 spent (<b>j</b>–<b>l</b>).</p>
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<p>TPR of the 3D printed catalysts.</p>
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