4.8 Article

Programmable Mechanically Assisted Geometric Deformations of Glassy Two-Stage Reactive Polymeric Materials

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 6, Issue 9, Pages 6111-6119

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/am405371r

Keywords

stimuli-responsive materials; photopatterning; shape memory; thiol-Michael addition; thiol isocyanate reaction

Funding

  1. National Science Foundation [DMR 1310528]
  2. Direct For Mathematical & Physical Scien
  3. Division Of Materials Research [1310528] Funding Source: National Science Foundation

Ask authors/readers for more resources

Thiol-isocyanate-methacrylate two-stage reactive network polymers were developed and used for fabrication of well-defined surface patterns as well as functional geometric shapes to demonstrate a new methodology for processing of smart materials. The dynamic stage I networks were synthesized in base-catalyzed thiol-isocyanate cross-linking reactions to yield tough, glassy materials at ambient conditions. Methacrylate-rich stage I networks, incorporating photoinitiator and photoabsorber, were irradiated with UV light to generate stage II networks with intricate property gradients. Upon directional straining and subsequent temperature-dependent stress relief of the predefined gradient regions, the desired surface or bulk geometric transformations were achieved. Depending on the gradient extent in conjunction with photoorthogonal initiators, the introduced deformations were shown to be easily erasable by heat or permanently fixable by bulk polymerization.

Authors

I am an author on this paper
Click your name to claim this paper and add it to your profile.

Reviews

Primary Rating

4.8
Not enough ratings

Secondary Ratings

Novelty
-
Significance
-
Scientific rigor
-
Rate this paper

Recommended

Article Chemistry, Multidisciplinary

Athermal, Chemically Triggered Release of RNA from Thioester Nucleic Acids

Sudheendran Mavila, Heidi R. Culver, Alex J. Anderson, Tania R. Prieto, Christopher N. Bowman

Summary: An athermal approach using self-immolative thioester linked nucleic acids (TENA) for mRNA enrichment from total RNA has shown comparable performance to a commercial kit. The method is compatible with downstream applications such as RT-qPCR for gene expression analysis.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Chemistry, Multidisciplinary

Shape Permanence in Diarylethene-Functionalized Liquid-Crystal Elastomers Facilitated by Thiol-Anhydride Dynamic Chemistry

Tayler S. Hebner, Maciej Podgorski, Sudheendran Mavila, Timothy J. White, Christopher N. Bowman

Summary: In this study, diarylethene-functionalized liquid-crystalline elastomers containing thiol-anhydride bonds were prepared and shown to exhibit reversible and reprogrammable photoinduced actuation. The generated strain could be reversed optically over multiple cycles, and the nematic director could be reprogrammed through heating. These findings have significant implications for the application of liquid-crystalline elastomers.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2022)

Article Polymer Science

Manipulating the Relative Rates of Reaction and Diffusion in a Holographic Photopolymer Based on Thiol-Ene Chemistry

Yunfeng Hu, Sudheendran Mavila, Maciej Podgorski, Jamie E. Kowalski, Robert R. McLeod, Christopher N. Bowman

Summary: This study investigates the effect of reaction and diffusion on the performance of thiol-ene-based holographic photopolymers. By controlling the rates of reaction and diffusion processes, the refractive index modulation and haze were evaluated. The results showed that changing the molecular weight of the polymer binder can vary the diffusion rate, while reducing the light intensity can decrease the reaction rate. Additionally, introducing a secondary thiol with slower reaction kinetics and a more stable thiyl radical can lower the refractive index modulation. An enhanced reactive binder with norbornene pendant groups was synthesized to achieve higher refractive index modulation at low light intensities.

MACROMOLECULES (2022)

Article Polymer Science

Spatial and Temporal Control of Photomediated Disulfide-Ene and Thiol-Ene Chemistries for Two-Stage Polymerizations

Shafer M. Soars, Nicholas J. Bongiardina, Benjamin D. Fairbanks, Maciej Podgorski, Christopher N. Bowman

Summary: A new strategy combining photomediated thiol-ene and disulfide-ene-based polymerization reactions is reported for the design and synthesis of high sulfur-containing materials for potential use in covalent adaptable networks and optical materials. By taking advantage of the relative reaction rates and semiorthogonally performing these reactions, controlled architecture polymer networks were produced. The study demonstrates the differential reaction rates between thiol-ene and disulfide-ene reactions, enabling spatial and temporal manipulation of material properties through dual-cure networks and photopatterning.

MACROMOLECULES (2022)

Article Polymer Science

Controlled Degradation of Cast and 3-D Printed Photocurable Thioester Networks via Thiol-Thioester Exchange

Juan J. Hernandez, Adam L. Dobson, Benjamin J. Carberry, Alexa S. Kuenstler, Parag K. Shah, Kristi S. Anseth, Timothy J. White, Christopher N. Bowman

Summary: This study examined and predicted the degradation of thioester-containing networks facilitated by base-catalyzed thiol-thioester exchange. A statistical model was developed and compared to experimental results, showing that degradation times could be controlled by varying reaction conditions. Thioester-based composite materials were successfully degraded, achieving high recovery of the composite filler.

MACROMOLECULES (2022)

Article Chemistry, Multidisciplinary

Photoinduced Dithiolane Crosslinking for Multiresponsive Dynamic Hydrogels

Benjamin R. Nelson, Bruce E. Kirkpatrick, Connor E. Miksch, Matthew D. Davidson, Nathaniel P. Skillin, Grace K. Hach, Alex Khang, Sydney N. Hummel, Benjamin D. Fairbanks, Jason A. Burdick, Christopher N. Bowman, Kristi S. Anseth

Summary: Researchers have developed a viscoelastic hydrogel with adaptable crosslinks to mimic time and position-dependent processes in tissues. By using 1,2-dithiolanes as dynamic covalent photocrosslinkers, the hydrogel can respond to multiple stimuli. Cell encapsulation is achieved through ligand-accelerated dithiolane ring-opening photopolymerization, enabling the study of 2D and 3D cell-material interactions.

ADVANCED MATERIALS (2023)

Article Polymer Science

The Contribution of Oligomerization Reaction Chemistry to the Thermomechanical Properties of Surface-Aligned Liquid Crystalline Elastomers

Timothy J. White, Tayler S. Hebner, Joselle M. McCracken, Christopher N. Bowman

Summary: Liquid crystalline elastomers (LCEs) exhibit large, directional deformation when aligned, and surface-enforced alignment enables complex 3-D shape transformations. Two-step reaction schemes, such as aza-Michael or thiol-Michael oligomerization followed by photopolymerization, have been commonly used to enforce orientation within LCEs. This study examines the impact of molecular weight on the stimulus response of LCEs, emphasizing its importance over the specific reaction used to form the oligomer.

MACROMOLECULES (2023)

Article Polymer Science

Catalytic Control of Crystallization in Dynamic Networks

Alexa S. Kuenstler, Christopher N. Bowman

Summary: The effect of varying nucleophilic strength of catalysts on thiol-thioester bond exchange dynamics and crystallization in a semicrystalline polymer network was investigated. The characteristic time scale of covalent bond exchange could be adjusted by changing the nucleophilicity of the catalyst. Crystallization kinetics were found to slow down with faster bond exchange rates, and a depression in melting temperature was observed with increasing bond exchange rate. Long-term DSC studies showed that bond exchange facilitated isothermal crystal rearrangement and growth.

ACS MACRO LETTERS (2023)

Article Multidisciplinary Sciences

Leaping liquid crystal elastomers

Tayler S. Hebner, Kevin Korner, Christopher N. Bowman, Kaushik Bhattacharya, Timothy J. White

Summary: This study demonstrates a rapid and powerful snap-through response in liquid crystalline elastomers (LCEs) by locally patterning the director orientation of LCEs and fabricating mechanical elements with through-thickness modulus gradients. The LCE elements exhibit a rapid acceleration and force output, enabling them to leap to heights over 200 times the material thickness in as fast as 6 ms.

SCIENCE ADVANCES (2023)

Article Nanoscience & Nanotechnology

Vat Photopolymerization Additive Manufacturing of Tough, Fully Recyclable Thermosets

Alexa S. Kuenstler, Juan J. Hernandez, Marianela Trujillo-Lemon, Alexander Osterbaan, Christopher N. Bowman

Summary: In order to advance additive manufacturing capabilities, novel resin formulations are required to produce high-fidelity parts with desired mechanical properties that can be easily recycled. This study presents a thiol-ene-based system incorporating semicrystallinity and dynamic thioester bonds to create polymer networks. The materials show ultimate toughness values >16 MJ cm(-3), similar to high-performance literature precedents. The treatment of these networks with excess thiols allows for thiol-thioester exchange, degrading polymerized networks into functional oligomers that can be repolymerized into constructs with varying thermomechanical properties.

ACS APPLIED MATERIALS & INTERFACES (2023)

Article Nanoscience & Nanotechnology

Discontinuous Metric Programming in Liquid Crystalline Elastomers

Tayler S. Hebner, Riley G. A. Bowman, Daniel Duffy, Cyrus Mostajeran, Itay Griniasty, Itai Cohen, Mark Warner, Christopher N. Bowman, Timothy J. White

Summary: Liquid crystalline elastomers (LCEs) are shape-changing materials that undergo large deformations in response to stimuli. By locally controlling the orientation of LCEs, we can achieve spontaneous shape changes in these materials. In this study, we propose a novel approach to shape-morphing in LCEs by spatially patterning the crosslink density to regulate the material deformation on a prescribed interface curve. We also develop a simple mathematical model to describe the behavior of LCEs. Through experiments and mathematical modeling, we demonstrate the control of Gaussian curvature and design self-cleaning LCEs based on temperature-dependent actuation properties.

ACS APPLIED MATERIALS & INTERFACES (2023)

Article Polymer Science

Dynamic Polymer Binder with Light-Regulated Molecular Weight via Addition-Fragmentation Chain Transfer for Holographic Recording

Yunfeng Hu, Maciej Podgorski, Sudheendran Mavila, Jasmine Sinha, Benjamin D. Fairbanks, Robert R. McLeod, Christopher N. Bowman

Summary: Dynamic covalent chemistry was employed to improve the holographic grating performance by facilitating diffusion of monomers and network rearrangement in a holographic photopolymer system. The radical-mediated addition-fragmentation chain transfer reaction between allyl sulfide (AS) moieties and thiols provided high spatiotemporal control, making it well-suited for high-quality holographic photopolymers. The exchange with a monofunctional thiol resulted in a significant decrease in molecular weight and viscosity, improving the recording formulations with limited diffusion of monomer and demonstrating a notable improvement of the refractive index modulation.

MACROMOLECULES (2023)

Article Chemistry, Multidisciplinary

Radical-Mediated Scission of Thioaminals for On-Demand Construction-Then-Destruction of Cross-Linked Polymer Networks

Juan J. Hernandez, Gopal Reddy Sama, Yunfeng Hu, Shafer Soars, Claire E. Niemet, Cassandra M. Sanchez, Christopher N. Bowman

Summary: Two-stage polymerizing-then-degrading networks are achieved by sequentially performing thiol-ene photopolymerization and radical-mediated thioaminal scission. Thioaminal scission occurs via ss-scission of the carbon next to the sulfur atom and is influenced by thiol substitution. Additionally, thioaminal scission occurs semi-orthogonally with the radical-mediated thiol-ene reaction.

ADVANCED FUNCTIONAL MATERIALS (2023)

Article Polymer Science

Adaptable Networks with Semiorthogonal Two-Stage Polymerizations Enabled by Sequential Photoinitiated Thiol-Ene and Disulfide-Ene Reactions

Yunfeng Hu, Shafer M. Soars, Bruce E. Kirkpatrick, Maciej Podgorski, Nicholas Bongiardina, Benjamin D. Fairbanks, Kristi S. Anseth, Christopher N. Bowman

Summary: This paper explores the utility of sequential thiol-ene and disulfide-ene photopolymerizations in materials applications such as shape fixation, photolithography, and holographic recording. By taking advantage of the significant difference in reaction rates between these two reactions, two-stage photopolymers with high specificity are formed. The dynamic behavior and shape fixation capabilities of these materials are demonstrated. The mechanical properties under stress are studied using techniques such as photolithography and polarized light microscopy. Additionally, the integrated network in the two-stage system is utilized for holographic grating recording with high refractive index modulation (Delta n) and low haze.

MACROMOLECULES (2023)

Article Polymer Science

Radical-disulfide exchange in thiol-ene-disulfidation polymerizations

Nicholas J. Bongiardina, Shafer M. Soars, Maciej Podgorski, Christopher N. Bowman

Summary: This study evaluated radical-disulfide exchange reactions in thiol-ene-disulfide networks using different thiol and disulfide containing monomers. The results show that the stress relaxation rate in these networks can be controlled by changing the thiol-disulfide stoichiometry or the disulfide type. The combination of different thiol and disulfide monomers also influences the polymerization rate of the thiol-ene reaction.

POLYMER CHEMISTRY (2022)

No Data Available