skip to main content


Title: Viscoelastic Characterization of Poly(3-hexylthiophene): Determination of Young’s Modulus
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 thin  more » « less
Award ID(s):
2219347
NSF-PAR ID:
10472072
Author(s) / Creator(s):
; ; ;
Editor(s):
Kirk S. Schanze, editor-in-chief
Publisher / Repository:
ACS Publications
Date Published:
Journal Name:
ACS Applied Polymer Materials
Volume:
5
Issue:
8
ISSN:
2637-6105
Page Range / eLocation ID:
6318 to 6324
Subject(s) / Keyword(s):
organic semiconductor mechanical properties nanoindentation Young’s modulus polymer film viscoelasticity.
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Debonding at the core–skin interphase region is one of the primary failure modes in core sandwich composites under shear loads. As a result, the ability to characterize the mechanical properties at the interphase region between the composite skin and core is critical for design analysis. This work intends to use nanoindentation to characterize the viscoelastic properties at the interphase region, which can potentially have mechanical properties changing from the composite skin to the core. A sandwich composite using a polyvinyl chloride foam core covered with glass fiber/resin composite skins was prepared by vacuum-assisted resin transfer molding. Nanoindentation at an array of sites was made by a Berkovich nanoindenter tip. The recorded nanoindentation load and depth as a function of time were analyzed using viscoelastic analysis. Results are reported for the shear creep compliance and Young’s relaxation modulus at various locations of the interphase region. The change of viscoelastic properties from higher values close to the fiber composite skin region to the smaller values close to the foam core was captured. The Young’s modulus at a given strain rate, which is also equal to the time-averaged Young’s modulus across the interphase region was obtained. The interphase Young’s modulus at a loading rate of 1 mN/s was determined to change from 1.4 GPa close to composite skin to 0.8 GPa close to the core. This work demonstrated the feasibility and effectiveness of nanoindentation-based interphase characterizations to be used as an input for the interphase stress distribution calculations, which can eventually enrich the design process of such sandwich composites. 
    more » « less
  2. ABSTRACT Polydopamine (PDA) is a biopolymer, which can form uniform thin films on almost all solid substrates as well as at the liquid/air interface. Carbonized polydopamine possesses graphite-like structure and exhibits high electrical conductivity, which makes it a potential carbon-based thin film conductor. However, studies on mechanical behavior of PDA and its derived materials are very limited. In this study, PDA samples were synthesized through self-assembly of dopamine in aqueous solution. Elastic modulus of thin films was measured using the nanoindentation technique. It is shown that the Young’s modulus of PDA thin film increased with increasing heat treatment temperature (up to 600°C). Doping with Cu ions also increased the Young’s modulus of PDA. Furthermore, all PDA thin films, with and without Cu, exhibited creep behavior. 
    more » « less
  3. Utilizing metal–organic frameworks (MOFs) as reinforcing fillers for polymer composites is a promising strategy because of the low density, high specific modulus, and tunable aspect ratio (AR). However, it has not been demonstrated for the MOF-reinforced polymer composite using MOFs with high AR and polymer-grafted surface, both of which are extremely important factors for efficient load transfer and favorable particle–matrix interaction. To this end, we designed an MOF–polymer composite system using high AR MOF PCN-222 as the mechanical reinforcer. Moreover, we developed a synthetic route to graft poly(methyl methacrylate) (PMMA) from the surface of PCN-222 through surface-initiated atomic transfer radical polymerization (SI-ATRP). The successful growth of PMMA on the surface of PCN-222 was confirmed via proton nuclear magnetic resonance and infrared spectroscopy. Through thermogravimetric analysis, the grafting density was found to be 0.18 chains/nm2. The grafted polymer molecular weight was controlled ranging from 50.3 to 158 kDa as suggested by size exclusion chromatography. Finally, we fabricated MOF–polymer composite films by the doctor-blading technique and measured the mechanical properties through the tension mode of dynamic mechanical analysis. We found that the mechanical properties of the composites were improved with increasing grafted PMMA molecular weight. The maximum reinforcement, a 114% increase in Young’s modulus at 0.5 wt % MOF loading in comparison to pristine PMMA films, was achieved when the grafted molecular weight was higher than the matrix molecular weight, which was in good agreement with previous literature. Moreover, our composite presents the highest reinforcement measured via Young’s modulus at low weight loading among MOF-reinforced polymer composites due to the high MOF AR and enhanced interface. Our approach offers great potential for lightweight mechanical reinforcement with high AR MOFs and a generalizable grafting-from strategy for porphyrin-based MOFs. 
    more » « less
  4. Vanadium oxide V3O5 exhibits an insulator-to-metal transition (IMT) near 430 K, which is the highest value for all vanadium oxides exhibiting IMTs. This makes it interesting for advanced electronic applications. However, the properties of V3O5 have been little studied, and, in particular, there are no reports of experimentally determined mechanical properties. In this work, Young’s modulus of sputter-deposited V3O5 thin films has been determined by measuring the fundamental resonant frequency of V3O5-coated silicon microcantilevers using a laser beam deflection technique. After deposition, the films were characterized by x-ray diffraction, resistivity measurements, and atomic force microscopy. The value of Young’s modulus experimentally determined for V3O5 was 198 ± 14 GPa, which is slightly lower than the computationally derived values for bulk crystal V3O5.

     
    more » « less
  5. Biocompatible and biodegradable materials have been used for fabricating polymeric microneedles to deliver therapeutic drug molecules through the skin. Microneedles have advantages over other drug delivery methods, such as low manufacturing cost, controlled drug release, and the reduction or absence of pain. The study examined the delivery of amphotericin B, an antifungal agent, using microneedles that were fabricated using a micromolding technique. The microneedle matrix was made from GantrezTM AN-119 BF, a benzene-free methyl vinyl ether/maleic anhydride copolymer. The GantrezTM AN-119 BF was mixed with water; after water evaporation, the polymer exhibited sufficient strength for microneedle fabrication. Molds cured at room temperature remained sharp and straight. SEM images showed straight and sharp needle tips; a confocal microscope was used to determine the height and tip diameter for the microneedles. Nanoindentation was used to obtain the hardness and Young’s modulus values of the polymer. Load–displacement testing was used to assess the failure force of the needles under compressive loading. These two mechanical tests confirmed the mechanical properties of the needles. In vitro studies validated the presence of amphotericin B in the needles and the antifungal properties of the needles. Amphotericin B GantrezTM microneedles fabricated in this study showed appropriate characteristics for clinical translation in terms of mechanical properties, sharpness, and antifungal properties. 
    more » « less