Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures

Street, Dayton P.; Ledford, William K.; Allison, Abigail A.; Patterson, Steven; Pickel, Deanna L.; Lokitz, Bradley S.; Messman, Jamie M.; Kilbey, S. Michael

doi:10.1021/acs.macromol.9b00546

Title: Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures

Abstract

Nonbonded interactions provide a way to guide the assembly and alter the physical properties of soft polymeric materials. The 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 mechanicalmore »« less

Authors:

Street, Dayton P. ^[1]; Ledford, William K. ^[1]; Allison, Abigail A. ^[2]; Patterson, Steven ^[3]; Pickel, Deanna L. ^[4];

^[5]; Messman, Jamie M. ^[3];

^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Chattanooga, TN (United States)
Honeywell Federal Manufacturing and Technologies, LLC, Kansas City, MO (United States)
Oak Ridge High School, Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:: Wed Jul 17 00:00:00 EDT 2019

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1545565

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 52; Journal Issue: 15; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Street, Dayton P., Ledford, William K., Allison, Abigail A., Patterson, Steven, Pickel, Deanna L., Lokitz, Bradley S., Messman, Jamie M., and Kilbey, S. Michael. Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.macromol.9b00546.

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                    Street, Dayton P., Ledford, William K., Allison, Abigail A., Patterson, Steven, Pickel, Deanna L., Lokitz, Bradley S., Messman, Jamie M., & Kilbey, S. Michael. Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures.  United States.  https://doi.org/10.1021/acs.macromol.9b00546

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                    Street, Dayton P., Ledford, William K., Allison, Abigail A., Patterson, Steven, Pickel, Deanna L., Lokitz, Bradley S., Messman, Jamie M., and Kilbey, S. Michael. Wed .  
"Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures".  United States.  https://doi.org/10.1021/acs.macromol.9b00546.  https://www.osti.gov/servlets/purl/1545565.

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@article{osti_1545565,

  title        = {Self-Complementary Multiple Hydrogen-Bonding Additives Enhance Thermomechanical Properties of 3D-Printed PMMA Structures},

  author       = {Street, Dayton P. and Ledford, William K. and Allison, Abigail A. and Patterson, Steven and Pickel, Deanna L. and Lokitz, Bradley S. and Messman, Jamie M. and Kilbey, S. Michael},

  abstractNote = {Nonbonded interactions provide a way to guide the assembly and alter the physical properties of soft polymeric materials. The 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.},

  doi          = {10.1021/acs.macromol.9b00546},

  journal      = {Macromolecules},

  number       = 15,

  volume       = 52,

  place        = {United States},

  year         = {Wed Jul 17 00:00:00 EDT 2019},

  month        = {Wed Jul 17 00:00:00 EDT 2019}

}

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https://doi.org/10.1021/acs.macromol.9b00546

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Cited by: 13 works

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Figures / Tables:

Figure 1: DMA results show an increase in Young’s modulus of all FFF-printed parts containing copolymer additives compared to the unmodified PMMA. Moreover, Young’s modulus increases as the UPyMA composition increases from 1 to 5 mol %. Values of Young’s modulus given in the legend are averages based on measurementsmore »

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