Current polymer network design suffers from intrinsic trade-offs, where polymer networks with high modulus often turn out to be in short of stretchability or fracture toughness. Here, we show a novel polymer network design through polymer-nanoparticle alternating hybrids that enable integrating the non-polymeric colloid deformation into polymer network design. The new class of polymer network exhibits colloidal yielding at small deformation before conformational change at higher elongation ratios, enabling simultaneous achievement of high Young’s modulus of E≈10-50 MPa, high yield strength of σ_Y~ 3-5 MPa, large stretchability of λ~7-10, and high fracture energy density of Γ~30 MJ/m^3. These results demonstrate a successful strategy to decouple the molecular mechanics for yield from that for stretchability or toughness, leading to new polymer networks design.
more »
« less
Multifaceted Shape Memory Polymer Technology for Biomedical Application: Combining Self-Softening and Stretchability Properties
Thiol-ene polymers are a promising class of biomaterials with a wide range of potential applications, including organs-on-a-chip, microfluidics, drug delivery, and wound healing. These polymers offer flexibility, softening, and shape memory properties. However, they often lack the inherent stretchability required for wearable or implantable devices. This study investigated the incorporation of di-acrylate chain extenders to improve the stretchability and conformability of those flexible thiol-ene polymers. Thiol-ene/acrylate polymers were synthesized using 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO), Trimethylolpropanetris (3-mercaptopropionate) (TMTMP), and Polyethylene Glycol Diacrylate (PEGDA) with different molecular weights (Mn 250 and Mn 575). Fourier Transform Infrared (FTIR) spectroscopy confirmed the complete reaction among the monomers. Uniaxial tensile testing demonstrated the softening and stretching capability of the polymers. The Young’s Modulus dropped from 1.12 GPa to 260 MPa upon adding 5 wt% PEGDA 575, indicating that the polymer softened. The Young’s Modulus was further reduced to 15 MPa under physiologic conditions. The fracture strain, a measure of stretchability, increased from 55% to 92% with the addition of 5 wt% PEGDA 575. A thermomechanical analysis further confirmed that PEGDA could be used to tune the polymer’s glass transition temperature (Tg). Moreover, our polymer exhibited shape memory properties. Our results suggested that thiol-ene/acrylate polymers are a promising new class of materials for biomedical applications requiring flexibility, stretchability, and shape memory properties.
more »
« less
- Award ID(s):
- 2237510
- PAR ID:
- 10473038
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Polymers
- Volume:
- 15
- Issue:
- 21
- ISSN:
- 2073-4360
- Page Range / eLocation ID:
- 4226
- Subject(s) / Keyword(s):
- thiol-ene/acrylate polymer shape memory polymer stretchable polymer flexible polymer polymer characterization conformal polymer self-softening polymer
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Cholesteric liquid crystals (CLCs) exhibit Bragg reflection due to their spontaneous self-assembly into a one-dimensional photonic structure. Retaining this cholesteric order in a polymer network requires functionalizing liquid crystals with reactive end groups. However, conventional chemistries for synthesizing cholesteric liquid crystalline polymers often result in poor surface alignment and reduced optical quality. In this work, we investigate a thiol−ene step-growth polymerization approach to fabricate cholesteric liquid crystalline elastomers (CLCEs) with tunable mechanical properties and improved optical quality. By varying the cross-link density, we systematically study the effects on haze, cross-linking degree, and mechanical response. Compared to existing cholesteric liquid crystalline polymers, the thiol−ene-based CLCEs exhibit enhanced surface alignment, reduced haze, and greater mechanical tunability. These materials are further benchmarked against CLCEs synthesized via thiol−acrylate chain transfer polymerization, highlighting the advantages of the thiol−ene reaction for achieving precisely controlled properties in cholesteric polymer networks.more » « less
-
Abstract Focused ultrasound (FUS) presents unique advantages for noninvasive localized heating, crucial for controlled shape recovery in shape memory polymers (SMPs), especially in biomedical applications. To enhance FUS-driven actuation efficiency, we propose boron nitride (BN)-infused SMP composites (SMPCs) tailored for targeted biomedical interventions. Using tert-butyl acrylate (tBA) and di(ethylene glycol) dimethacrylate as base materials, we integrated BN fillers at varying concentrations (1, 5, and 10 wt.%). A thorough characterization was carried out, including dynamic mechanical analysis, scanning electron microscopy, uniaxial tensile testing, and swelling study. These results show that increasing the BN content improves shape recovery efficiency significantly. Specifically, the 10 wt.% BN composites outperformed plain SMP in terms of shape recovery ratio when activated with FUS, and the highest shape recovery ratio can achieve 75%. However, higher BN content decreases crosslinking density and stiffness, as shown by a lower Young’s modulus and glass transition temperature. This study demonstrates the promise of BN-infused SMPCs for advanced applications in biomedical application, where noninvasive spatiotemporal actuation of SMPs is required.more » « less
-
Engineering applications of current thermoset shape memory polymers are limited by three critical issues: demanding fabrication conditions (from 70 to 300 °C temperatures for hours or days), lack of reprocessability or recyclability, and low recovery stress and energy output. To address these problems simultaneously, a new UV curable and vitrimer-based epoxy thermoset shape memory polymer (VSMP) has been synthesized. A 1.1 mm thick VSMP film can be readily cured at room temperature under UV-irradiation (61 mW cm −2 ) in just 80 s. It possesses 36.7 MPa tensile strength, 230 MPa compressive strength, and 3120 MPa modulus at room temperature. It still has a compressive strength of 187 MPa at 120 °C. The covalent adaptable network (CAN) imparts the VSMP with recyclability, as reflected by two effective recycling cycles (>60% recycling efficiency). In addition, the VSMP exhibits good shape memory properties for multiple shape recovery cycles. With 20% compression programming strain, up to 13.4 MPa stable recovery stress and 1.05 MJ m −3 energy output in the rubbery state are achieved. With good mechanical strength, thermal stability, recyclability, and excellent shape memory properties combined with in situ UV-curing capabilities, the new VSMP is a promising multifunctional thermoset for engineering applications.more » « less
-
Kirk S. Schanze, editor-in-chief (Ed.)Nanoindentation is an optimal technique for the measurement of thin film mechanical properties. Polymers present a unique problem in that their response to loading is time-dependent. Due to this, many of the most common nanoindentation methods are not suitable for probing polymer nanoscale properties. Despite this issue being well-known for decades, poly(3-hexylthiophene) has been exclusively analyzed by time-independent mechanical properties testing methods. Herein, we present a nanoindentation technique that analyzes the materials’ time-dependent response under both constant rate loading and step loading. By determining viscoelastic functions, we are able to extract the Young’s relaxation modulus of poly(3- hexylthiophene). The average Young’s modulus acquired from viscoelastic nanoindentation is determined to be 260 ± 27 MPa. These results are in excellent agreement with specialized mechanical tests for thinmore » « less
An official website of the United States government

