ACS Publications. Most Trusted. Most Cited. Most Read
Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2019, 52, 15, 5574-5582
    Article

    Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures
    Click to copy article linkArticle link copied!

    • Dayton P. Street
      Dayton P. Street
      Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by Dayton P. Street
    • William K. Ledford
      William K. Ledford
      Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
      More by William K. Ledford
    • Abigail A. Allison
      Abigail A. Allison
      Department of Chemical Engineering, University of Tennessee, Chattanooga, Tennessee 37403, United States
      More by Abigail A. Allison
    • Steven Patterson
      Steven Patterson
      Honeywell Federal Manufacturing and Technologies, LLC, Kansas City, Missouri 64147, United States
      More by Steven Patterson
    • Deanna L. Pickel
      Deanna L. Pickel
      Oak Ridge High School, Oak Ridge, Tennessee 37830, United States
      More by Deanna L. Pickel
    • Bradley S. Lokitz
      Bradley S. Lokitz
      Center for Nanophase Materials Sciences, Oak Ridge National Lab, Oak Ridge, Tennessee 37831, United States
      More by Bradley S. Lokitz
      Orcidhttp://orcid.org/0000-0002-1229-6078
    • Jamie M. Messman
      Jamie M. Messman
      Honeywell Federal Manufacturing and Technologies, LLC, Kansas City, Missouri 64147, United States
      More by Jamie M. Messman
    • S. Michael Kilbey II*
      S. Michael Kilbey, II
      Department of Chemistry  and  Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States
      *E-mail: [email protected]
      More by S. Michael Kilbey, II
      Orcidhttp://orcid.org/0000-0002-9431-1138
    Other Access OptionsSupporting Information (1)

    Macromolecules

    Cite this: Macromolecules 2019, 52, 15, 5574–5582
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b00546
    Published July 17, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Nonbonded interactions provide a way to guide the assembly and alter the physical properties of soft polymeric materials. Here, self-complementary hydrogen-bonding interactions conveyed through polymeric additives dramatically enhance thermomechanical properties of poly(methyl methacrylate) (PMMA) specimens printed by fused filament fabrication (FFF). Random copolymer additives composed of methyl methacrylate (MMA) and a methacrylate monomer containing 2-ureido-4-pyrimidone (UPy) pendant group (UPyMA), which self-dimerize through quadruple hydrogen-bonding interactions, were incorporated at 1 wt % in a high molecular weight PMMA matrix. Results from dynamic mechanical analysis measurements made in the glassy regime show that as the UPyMA comonomer content in the p(MMA-r-UPyMA) copolymer additive increases up to 5 mol %, there is a 50% increase in Young’s modulus and a 62% increase in the storage modulus. Concomitantly, there is an 85% increase in ultimate tensile strength and a 100% increase in tensile modulus. Additionally, rheology measurements indicate that at temperatures well above the glass transition temperature, the storage modulus and complex viscosity of the multicomponent blends are unaffected by the incorporation of p(MMA-r-UPyMA) additives, regardless of the UPyMA content. In aggregate, these results suggest that using reversible, nonbonded intermolecular interactions, such as multidentate hydrogen bonding, provides a novel route to overcome the mechanical property limitations of FFF-printed materials without affecting melt processability.

    Copyright © 2019 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.9b00546.

    • 1H NMR spectra of the UPy methacrylate monomer and copolymers made by free radical polymerization; GPC traces of copolymers; characteristics of PMMA multicomponent filaments; images of FFF-printed DMA and tensile specimens; frequency shift factors generated by time–temperature superposition; DMA measurements examining the thermomechanical properties of PMMA blends containing a PMMA homopolymer additive; and representative master curves from small-amplitude oscillatory shear rheology showing the relationship between G′(ω) and G″(ω) (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 29 publications.

    1. Meijia Gong, Luping Wang, Kaiyang Hou, Kaiqiang Zhang, Xu Wang. Mastering Hydrogen Bonding at Hard–Soft Interfaces for Ultrahigh Damage Resistance in Elastomers. Macromolecules 2025, 58 (6) , 3241-3254. https://doi.org/10.1021/acs.macromol.5c00002
    2. Seungjun Kim, Soeun Park, Min Su Kim, Hyeonji Lee, Hyeji Lee, Keun Hyung Lee, Myungwoong Kim. Supramolecular Association of a Block Copolymer via Strong Hydrogen Bonding to Form Self-Healable Ionogels. ACS Applied Materials & Interfaces 2024, 16 (38) , 51459-51468. https://doi.org/10.1021/acsami.4c09988
    3. Qingyu Niu, Hang Han, Huanrong Li, Zhiqiang Li. Room-Temperature Self-Healing Glassy Luminescent Hybrid Film. Langmuir 2023, 39 (17) , 5979-5985. https://doi.org/10.1021/acs.langmuir.2c03300
    4. Benjamin M. Yavitt, Lutz Wiegart, Daniel Salatto, Zhixing Huang, Leonidas Tsapatsaris, Maya K. Endoh, Sascha Poeller, Manuel Schiel, Stanislas Petrash, Tadanori Koga. Spatial-Temporal Dynamics at the Interface of 3D-Printed Photocurable Thermoset Resin Layers. ACS Applied Engineering Materials 2023, 1 (2) , 868-876. https://doi.org/10.1021/acsaenm.2c00248
    5. Subarna Samanta, Sungjin Kim, Tomonori Saito, Alexei P. Sokolov. Polymers with Dynamic Bonds: Adaptive Functional Materials for a Sustainable Future. The Journal of Physical Chemistry B 2021, 125 (33) , 9389-9401. https://doi.org/10.1021/acs.jpcb.1c03511
    6. Xinshuai Gao, Honghua Wang, Xu Zhang, Xinming Gu, Yuzhe Liu, Guangyuan Zhou, Shifang Luan. Preparation of Amorphous Poly(aryl ether nitrile ketone) and Its Composites with Nano Hydroxyapatite for 3D Artificial Bone Printing. ACS Applied Bio Materials 2020, 3 (11) , 7930-7940. https://doi.org/10.1021/acsabm.0c01044
    7. Sang Cheon Lee, Gregory Gillispie, Peter Prim, Sang Jin Lee. Physical and Chemical Factors Influencing the Printability of Hydrogel-based Extrusion Bioinks. Chemical Reviews 2020, 120 (19) , 10834-10886. https://doi.org/10.1021/acs.chemrev.0c00015
    8. Chase B. Thompson, LaShanda T. J. Korley. 100th Anniversary of Macromolecular Science Viewpoint: Engineering Supramolecular Materials for Responsive Applications—Design and Functionality. ACS Macro Letters 2020, 9 (9) , 1198-1216. https://doi.org/10.1021/acsmacrolett.0c00418
    9. Dayton P. Street, Adeline Huizhen Mah, William K. Ledford, Steven Patterson, James A. Bergman, Bradley S. Lokitz, Deanna L. Pickel, Jamie M. Messman, Gila E. Stein, S. Michael Kilbey II. Tailoring Interfacial Interactions via Polymer-Grafted Nanoparticles Improves Performance of Parts Created by 3D Printing. ACS Applied Polymer Materials 2020, 2 (3) , 1312-1324. https://doi.org/10.1021/acsapm.9b01195
    10. Uchenna C. Obi, Emmanuel O. Onche, Odette Fayen Ngasoh, Farshad Barzegar, Blessing Nneka Ekwe, Azikiwe Peter Onwualu, Abdulhakeem Bello. Polymer electrolytes for enhanced mechanical integrity in lithium-ion batteries: a review of recent progress and future directions. Journal of Polymer Engineering 2025, 45 (5) , 375-387. https://doi.org/10.1515/polyeng-2024-0200
    11. Tristan Tenio, Solomon Boakye-Yiadom. Characterization and selection of a skull surrogate for the development of a biofidelic head model. Journal of the Mechanical Behavior of Biomedical Materials 2024, 158 , 106680. https://doi.org/10.1016/j.jmbbm.2024.106680
    12. John D. Kechagias, Stephanos P. Zaoutsos, Nikolaos A. Fountas, Nikolaos M. Vaxevanidis. Experimental investigation and neural network development for modeling tensile properties of polymethyl methacrylate (PMMA) filament material. The International Journal of Advanced Manufacturing Technology 2024, 134 (9-10) , 4387-4398. https://doi.org/10.1007/s00170-024-14402-0
    13. Bevan Harbinson, Sierra F. Yost, Bryan D. Vogt. Surface topology as non-destructive proxy for tensile strength of plastic parts from filament-based material extrusion. Progress in Additive Manufacturing 2024, 9 (4) , 1105-1117. https://doi.org/10.1007/s40964-023-00506-8
    14. Alberto Andreu, Haeseung Lee, Jiheong Kang, Yong‐Jin Yoon. Self‐Healing Materials for 3D Printing. Advanced Functional Materials 2024, 34 (30) https://doi.org/10.1002/adfm.202315046
    15. Sierra F. Yost, Christian W. Pester, Bryan D. Vogt. Molecular mass engineering for filaments in material extrusion additive manufacture. Journal of Polymer Science 2024, 62 (12) , 2616-2629. https://doi.org/10.1002/pol.20230559
    16. Jia-Ruey Ai, Seokhoon Jang, Wyatt Fink, Seong H. Kim, Bryan D. Vogt. Role of polymer interactions in core–shell filaments in the mechanical properties of 3D printed objects. RSC Applied Polymers 2024, 2 (1) , 105-116. https://doi.org/10.1039/D3LP00168G
    17. Na Chen. Embedded 3D printing and pressurized thermo-curing of PMMA for medical implants. Journal of the Mechanical Behavior of Biomedical Materials 2023, 146 , 106083. https://doi.org/10.1016/j.jmbbm.2023.106083
    18. Larissa Alena Ruppitsch, Jakob Ecker, Thomas Koch, Katharina Ehrmann, Jürgen Stampfl, Robert Liska. Dynamic monomers for Hot Lithography: The UPy motif as a versatile tool towards stress relaxation, reprocessability, and 3D printing. Journal of Polymer Science 2023, 61 (13) , 1318-1334. https://doi.org/10.1002/pol.20220721
    19. Lan-Yun Chen, Lu Wei, Yu Hai, Li-Juan Liu, Kang-Da Zhang, Tian-Guang Zhan. Construction of photoswitchable urea-based multiple H-bonding motifs. Tetrahedron 2023, 136 , 133343. https://doi.org/10.1016/j.tet.2023.133343
    20. William K. Ledford, S. Michael Kilbey. Impact of hydrogen bonding pendant groups in polymer grafted nanoparticles on interlayer adhesion and mechanical properties in material extrusion printing. Additive Manufacturing 2023, 63 , 103419. https://doi.org/10.1016/j.addma.2023.103419
    21. Xinzhe Xue, Dun Lin, Yat Li. Low Tortuosity 3D‐Printed Structures Enhance Reaction Kinetics in Electrochemical Energy Storage and Electrocatalysis. Small Structures 2022, 3 (12) https://doi.org/10.1002/sstr.202200159
    22. Yu-Cheng Ju, Donyau Chiang, Ming-Yen Tsai, Hao Ouyang, Sanboh Lee. Stress Relaxation Behavior of Poly(Methyl Methacrylate)/Graphene Composites: Ultraviolet Irradiation. Polymers 2022, 14 (19) , 4192. https://doi.org/10.3390/polym14194192
    23. Lu-Ping Wang, Ming-Guang Zhang, Jing-Cheng Hao, Xu Wang. Insertion of Supramolecular Segments into Covalently Crosslinked Polyurethane Networks towards the Fabrication of Recyclable Elastomers. Chinese Journal of Polymer Science 2022, 40 (3) , 321-330. https://doi.org/10.1007/s10118-022-2651-2
    24. A.D. O'Donnell, S. Salimi, L.R. Hart, T.S. Babra, B.W. Greenland, W. Hayes. Applications of supramolecular polymer networks. Reactive and Functional Polymers 2022, 172 , 105209. https://doi.org/10.1016/j.reactfunctpolym.2022.105209
    25. Shi‐Tao Han, Hong‐Ying Duan, Lan‐Yun Chen, Tian‐Guang Zhan, Li‐Juan Liu, Li‐Chun Kong, Kang‐Da Zhang. Photo‐Controlled Macroscopic Self‐Assembly Based on Photo‐Switchable Hetero‐Complementary Quadruple Hydrogen Bonds. Chemistry – An Asian Journal 2021, 16 (23) , 3886-3889. https://doi.org/10.1002/asia.202101076
    26. Harald Rupp, Wolfgang H. Binder. 3D Printing of Solvent-Free Supramolecular Polymers. Frontiers in Chemistry 2021, 9 https://doi.org/10.3389/fchem.2021.771974
    27. William K. Ledford, Sina Sabury, S. Michael Kilbey. Enhancing nanomaterial dispersion and performance of parts printed via FFF by a solution casting method. MRS Communications 2021, 11 (2) , 122-128. https://doi.org/10.1557/s43579-020-00008-6
    28. Lu Wei, Shi-Tao Han, Ting-Ting Jin, Tian-Guang Zhan, Li-Juan Liu, Jiecheng Cui, Kang-Da Zhang. Towards photoswitchable quadruple hydrogen bonds via a reversible “photolocking” strategy for photocontrolled self-assembly. Chemical Science 2021, 12 (5) , 1762-1771. https://doi.org/10.1039/D0SC06141G
    29. Guangpu Zhang, Zhe Sun, Miaomiao Li, , , . Recent developments: self-healing polymers based on quadruple hydrogen bonds. E3S Web of Conferences 2021, 290 , 01037. https://doi.org/10.1051/e3sconf/202129001037
    Download PDF
    Go to Macromolecules
    Get e-Alerts
    Get e-Alerts

    Macromolecules

    Cite this: Macromolecules 2019, 52, 15, 5574–5582
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.9b00546
    Published July 17, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

    Article Views

    2257

    Altmetric

    -

    Citations

    29
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.