skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Integrated colloidal deformation to advanced polymer network design through polymer-nanoparticle alternating hybrids
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
Award ID(s):
2211573
PAR ID:
10503521
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Giant
Volume:
17
Issue:
C
ISSN:
2666-5425
Page Range / eLocation ID:
100218
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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
  2. ynthesis-property relation is fundamental to materials science, but many aspects of the relation are not well understood for many materials. Impetus for this paper comes from our recent appreciation for the distinct roles of entanglements and crosslinks in a polymer network. Here we study the synthesis-property relation of polyacrylamide hydrogels prepared by free radical polymerization. Some of the as-prepared hydrogels are further submerged in water to swell either to equilibrium or to a certain polymer content. The synthesis parameters include the composition of a precursor, as well as the polymer content of a hydrogel. Series of hydrogels are prepared along several paths in the space of synthesis parameters. For each hydrogel, the stress-stretch curve is measured, giving four properties: modulus, strength, stretchability, and work of fracture. We interpret the experimentally measured synthesis-property relation in terms of entropic polymer networks of covalent bonds. When the precursor has a low crosslinker-to-monomer molar ratio, the resulting polymer network has on average long polymer segments. When the precursor has a low water-to-monomer molar ratio, the resulting polymer network has on average many entanglements per polymer segment. We show that crosslinks lower strength, but entanglements do not. By contrast, both crosslinks and entanglements increase modulus. A network of highly entangled long polymer segments exhibits high swell resistance, modulus, and strength. 
    more » « less
  3. Abstract Wearable devices benefit from the use of stretchable conjugated polymers (CPs). Traditionally, the design of stretchable CPs is based on the assumption that a low elastic modulus (E) is crucial for achieving high stretchability. However, this research, which analyzes the mechanical properties of 65 CP thin films, challenges this notion. It is discovered that softness alone does not determine stretchability; rather, it is the degree of entanglement that is critical. This means that rigid CPs can also exhibit high stretchability, contradicting conventional wisdom. To inverstigate further, the mechanical behavior, electrical properties, and deformation mechanism of two model CPs: a glassy poly(3‐butylthiophene‐2,5‐diyl) (P3BT) with anEof 2.2 GPa and a viscoelastic poly(3‐octylthiophene‐2,5‐diyl) (P3OT) with anEof 86 MPa, are studied. Ex situ transmission X‐ray scattering and polarized UV–vis spectroscopy revealed that only the initial strain (i.e., <20%) exhibits different chain alignment mechanisms between two polymers, while both rigid and soft P3ATs showed similarly behavior at larger strains. By challenging the conventional design metric of lowEfor high stretchability and highlighting the importance of entanglement, it is hoped to broaden the range of CPs available for use in wearable devices. 
    more » « less
  4. Abstract For wearable and implantable electronics applications, developing intrinsically stretchable polymer semiconductor is advantageous, especially in the manufacturing of large‐area and high‐density devices. A major challenge is to simultaneously achieve good electrical and mechanical properties for these semiconductor devices. While crystalline domains are generally needed to achieve high mobility, amorphous domains are necessary to impart stretchability. Recent progresses in the design of high‐performance donor–acceptor polymers that exhibit low degrees of energetic disorder, while having a high fraction of amorphous domains, appear promising for polymer semiconductors. Here, a low crystalline, i.e., near‐amorphous, indacenodithiophene‐co‐benzothiadiazole (IDTBT) polymer and a semicrystalline thieno[3,2‐b]thiophene‐diketopyrrolopyrrole (DPPTT) are compared, for mechanical properties and electrical performance under strain. It is observed that IDTBT is able to achieve both a high modulus and high fracture strain, and to preserve electrical functionality under high strain. Next, fully stretchable transistors are fabricated using the IDTBT polymer and observed mobility ≈0.6 cm2V−1s−1at 100% strain along stretching direction. In addition, the morphological evolution of the stretched IDTBT films is investigated by polarized UV–vis and grazing‐incidence X‐ray diffraction to elucidate the molecular origins of high ductility. In summary, the near‐amorphous IDTBT polymer signifies a promising direction regarding molecular design principles toward intrinsically stretchable high‐performance polymer semiconductor. 
    more » « less
  5. null (Ed.)
    Alignment of highly anisotropic nanomaterials in a polymer matrix can yield nanocomposites with unique mechanical and transport properties. Conventional methods of nanocomposite film fabrication are not well-suited for manufacturing composites with very high concentrations of anisotropic nanomaterials, potentially limiting the widespread implementation of these useful structures. In this work, we present a scalable approach to fabricate polymer-infiltrated nanoplatelet films (PINFs) based on flow coating and capillary rise infiltration (CaRI) and study the processing–structure–property relationship of these PINFs. We show that films with high aspect ratio (AR) gibbsite (Al (OH) 3 ) nanoplatelets (NPTs) aligned parallel to the substrate can be prepared using a flow coating process. NPTs are highly aligned with a Herman's order parameter of 0.96 and a high packing fraction >80 vol%. Such packings show significantly higher fracture toughness compared to low AR nanoparticle (NP) packings. By depositing NPTs on a polymer film and subsequently annealing the bilayer above the glass transition temperature of the polymer, polymer infiltrates into the tortuous NPT packings though capillarity. We observe larger enhancement in the modulus, hardness and scratch resistance of NPT films upon polymer infiltration compared to NP packings. The excellent mechanical properties of such films benefit from both thermally promoted oxide bridge formation between NPTs as well as polymer infiltration increasing the strength of NPT contacts. Our approach is widely applicable to highly anisotropic nanomaterials and allows the generation of mechanically robust polymer nanocomposite films for a diverse set of applications. 
    more » « less