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: Topological effect on mechanical properties of self-assembled block copolymer
Herein, this work aims to demonstrate the topological effect on the mechanicalx characteristics of selfassembled block copolymers (BCPs). The lamellae-forming polystyrene- block -polydimethylsiloxane (PSb -PDMS) can be self-assembled into various nanostructured monoliths with the use of PS-selective solvent for solvent annealing, giving diamond, gyroid, and cylinder structures with increasing the swelling degree of PS domain (the effective volume fraction of the PS segment after solvent annealing followed by evaporation). The stiffness of the self-assembled monoliths is scrutinized by nanoindentation test. For intrinsic PS- b -PDMS monolith with lamellar structure, the reduced elastic modulus as calculated from the measured stiffness is 0.91 GPa. By contrast, the PS- b -PDMS monolith with cylinder structure gives a significant reduction in reduced elastic modulus with the value of 0.52 GPa due to the introduced microporosity to the PS domain from solvent annealing using PS-selective solvent, resulting in the lower confrontation for continuous layer-by-layer deformation of hard PS and soft PDMS domains. In the case of gyroid-structured PS- b -PDMS monolith, it is unexpected to exhibit a significant increase in the reduced elastic modulus with a value of 1.6 GPa: note that the effect of microporosity is still significant. Accordingly, the enhancement of the reduced elastic modulus is attributed to the effect of deliberate structuring with network topology ( i.e., three-dimensional co-continuous hard PS and soft PDMS domains) that is able to hold the occurrence of large-scale deformation. In contrast to the gyroid with a three-strut texture, the diamond-structured PS- b -PDMS monolith with a four-strut texture is superior to the gyroid with a reduced elastic modulus of 2.2 GPa, further confirming the suggested topology effect.  more » « less
Award ID(s):
2105296
PAR ID:
10511719
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Publisher / Repository:
Elsevier
Date Published:
Journal Name:
Giant
Volume:
17
Issue:
C
ISSN:
2666-5425
Page Range / eLocation ID:
100205
Subject(s) / Keyword(s):
Block copolymer, Self-assembly, Topology effect, Thin film, Nanoindentation, Reduced elastic modulus
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. none (Ed.)
    Abstract By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface‐to‐volume ratio. Here, the theoretically limited structural volume of the DG phase in coil‐coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra‐high porosities. The new materials design, dual‐extractable nanocomposite, is created by incorporating a photodegradable block with a solvent‐extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface‐to‐volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface‐to‐volume ratio, being applicable for nanotemplate‐synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties. 
    more » « less
  2. ABSTRACT We demonstrate the directional alignment of perpendicular‐lamellae domains in fluorinated three‐armed star block polymer (BP) thin films using solvent vapor annealing with shear stress. The control of orientation and alignment was accomplished without any substrate surface modification. Additionally, three‐armed star poly(methyl methacrylate‐block‐styrene) [PMMA‐PS] and poly(octafluoropentyl methacrylate‐block‐styrene) were compared to their linear analogues to examine the impact of fluorine content and star architecture on self‐assembled BP feature sizes and interdomain density profiles. X‐ray reflectometry results indicated that the star BP molecular architecture increased the effective polymer segregation strength and could possibly facilitate reduced polymer domain spacings, which are useful in next‐generation nanolithographic applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2019, 57, 1663–1672 
    more » « less
  3. null (Ed.)
    Abstract Rapid thermokinetics associated with laser-based additive manufacturing produces strong bulk crystallographic texture in the printed component. The present study identifies such a bulk texture effect on elastic anisotropy in laser powder bed fused Ti6Al4V by employing an effective bulk modulus elastography technique coupled with ultrasound shear wave velocity measurement at a frequency of 20 MHz inside the material. The combined technique identified significant attenuation of shear velocity from 3322 ± 20.12 to 3240 ± 21.01 m/s at 45 $$^\circ$$ ∘ and 90 $$^\circ$$ ∘ orientations of shear wave plane with respect to the build plane of printed block of Ti6Al4V. Correspondingly, the reduction in shear modulus from 48.46 ± 0.82 to 46.40 ± 0.88 GPa was obtained at these orientations. Such attenuation is rationalized based on the orientations of $$\alpha ^\prime$$ α ′ crystallographic variants within prior columnar $$\beta$$ β grains in additively manufactured Ti6Al4V. 
    more » « less
  4. A new type of high-entropy alloy, a nitride-based (AlCrTiZrMo)N/ZrO2 nano-multilayered film, was designed to investigate the effect of ZrO2 layer thickness on the microstructure, mechanical properties, and thermal stability. The results show that when the thickness of the ZrO2 layer is less than 0.6 nm, it can be transformed into cubic-phase growth under the template effect of the (AlCrTiZrMo)N layer, resulting in an increased hardness. The (AlCrTiZrMo)N/ZrO2 film with a ZrO2 layer thickness of 0.6 nm has the highest hardness and elastic modulus of 35.1 GPa and 376.4 GPa, respectively. As the thickness of the ZrO2 layer further increases, ZrO2 cannot maintain the cubic structure, and the epitaxial growth interface is destroyed, resulting in a decrease in hardness. High-temperature annealing treatments indicate that the mechanical properties of the film decrease slightly after annealing at less than 900 °C for 30 min, while the mechanical properties decrease significantly after annealing for 30 min at 1000–1100 °C. The hardness and elastic modulus after annealing at 900 °C are still 24.5 GPa and 262.3 GPa, showing excellent thermal stability. This conclusion verifies the “template” effect of the nano-multilayered film, which improves the hardness and thermal stability of the high-entropy alloy. 
    more » « less
  5. Nanoindentation coupled with Atomic Force Microscopy was used to study stiffness, hardness, and the reduced Young’s modulus of reduced graphene oxide. Oxygen reduction on the graphene oxide sample was performed via LightScribe DVD burner reduction, a cost-effective approach with potential for large scale graphene production. The reduction of oxygen in the graphene oxide sample was estimated to about 10 percent using FTIR spectroscopic analysis. Images of the various samples were captured after each reduction cycle using Atomic Force Microscopy. Elastic and spectroscopic analyses were performed on the samples after each oxygen reduction cycle in the LightScribe, thus allowing for a comparison of stiffness, hardness, and the reduced Young’s modulus based on the number of reduction cycles. The highest values obtained were after the fifth and final reduction cycle, yielding a stiffness of 22.4 N/m, a hardness of 0.55 GPa, and a reduced Young’s modulus of 1.62 GPa as compared to a stiffness of 22.8 N/m, a hardness of 0.58 GPa, and a reduced Young’s modulus of 1.84 GPa for a commercially purchased graphene film made by CVD. This data was then compared to the expected values of pristine single layer graphene. Furthermore, two RC circuits were built, one using a parallel plate capacitors made of light scribed graphene on a kapton substrate (LSGC) and a second one using a CVD deposited graphene on aluminum (CVDGC). Their RC time constants and surface charge densities were compared. 
    more » « less