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: Comparison of nanocrystalline cellulose dispersion versus surface nucleation in poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) crystallization
Abstract Nanocrystalline cellulose (NCC), which is a known crystal nucleating agent, is utilized to improve poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) thermal properties. Since NCC aggregation in PHBV negatively affects composite properties and processability, NCC crystal nucleation effectiveness was examined at low concentrations (<1%) under isothermal and nonisothermal conditions. NCC was dispersed in PHBV solutions using a solvent exchange method and then cast into films. We found that NCC was an effective nucleating agent in amounts as low as 0.25%, resulting in an increase in PHBV crystallization rate by more than 50%. However, increasing to 1% NCC resulted in aggregation in PHBV, with the NCC becoming less effective compared to lower NCC concentrations. In an attempt to improve NCC dispersion, we added cellulose acetate (CA) or stearic acid (SA) to the casting solution, anticipating that CA or SA would preferentially adsorb on the NCC. With such pretreatment, dispersion was indeed improved but NCC became less effective as a PHBV nucleating agent. This work shows the advantage of using low NCC concentrations (<0.5%) for promoting PHBV crystallization, but the lack of improved nucleation upon addition of CA and SA supports the importance of NCC surface accessibility.  more » « less
Award ID(s):
1727836
PAR ID:
10455159
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
SPE Polymers
Volume:
1
Issue:
1
ISSN:
2690-3857
Format(s):
Medium: X Size: p. 15-25
Size(s):
p. 15-25
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Cirrus ice crystals are produced heterogeneously on ice‐nucleating particles (INPs) and homogeneously in supercooled liquid solution droplets. They grow by uptake of water molecules from the ice‐supersaturated vapor. The precursor particles, characterized by disparate ice nucleation abilities and number concentrations, compete for available vapor during ice formation events. We investigate cirrus formation events systematically in different temperature and updraft regimes, and for different INP number concentrations and time‐independent nucleation efficiencies. We consider vertical air motion variability due to mesoscale gravity waves and effects of supersaturation‐dependent deposition coefficients for water molecules on ice surfaces. We analyze ice crystal properties to better understand the dynamics of competing nucleation processes. We study the reduction of ice crystal numbers produced by homogeneous freezing due to INPs in both, individual simulations assuming constant updraft speeds and in ensemble simulations based on a stochastic representation of vertical wind speed fluctuations. We simulate and interpret probability distributions of total nucleated ice crystal number concentrations, showing signatures of homogeneous and heterogeneous nucleation. At typically observed, mean updraft speeds (≈15 cm s−1) competing nucleation should occur frequently, even at rather low INP number concentrations (<10 L−1). INPs increase cirrus occurrence and may alter cirrus microphysical properties without entirely suppressing homogeneous freezing events. We suggest to improve ice growth models, especially for low cirrus temperatures (<220 K) and low ice supersaturation (<0.3). 
    more » « less
  2. Abstract Optoelectronics are crucial for developing energy‐efficient chip technology, with phase‐change materials (PCMs) emerging as promising candidates for reconfigurable components in photonic integrated circuits, such as nonvolatile phase shifters. Antimony sulfide (Sb2S3) stands out due to its low optical loss and considerable phase‐shifting properties, along with the non‐volatility of both phases. This study demonstrates that the crystallization kinetics of Sb2S3can be switched from growth‐driven to nucleation‐driven by altering the sample dimension from bulk to film. This tuning of the crystallization process is critical for optical switching applications requiring control over partial crystallization. Calorimetric measurements with heating rates spanning over six orders of magnitude, reveal that, unlike conventional PCMs that crystallize below the glass transition, Sb2S3exhibits a measurable glass transition prior to crystallization from the undercooled liquid (UCL) phase. The investigation of isothermal crystallization kinetics provides insights into nucleation rates and crystal growth velocities while confirming the shift to nucleation‐driven behavior at reduced film thicknesses—an essential aspect for effective device engineering. A fundamental difference in chemical bonding mechanisms was identified between Sb2S3, which exhibits covalent bonding in both material phases, and other PCMs, such as GeTe and Ge2Sb2Te5, which demonstrate pronounced bonding alterations upon crystallization. 
    more » « less
  3. Aerosols affect cirrus formation and evolution, yet quantification of these effects remain difficult based on in-situ observations due to the complexity of nucleation mechanisms and large variabilities in ice microphysical properties. This work employed a method to distinguish five evolution phases of cirrus clouds based on in-situ aircraft-based observations from seven U.S. National Science Foundation (NSF) and five NASA flight campaigns. Both homogeneous and heterogeneous nucleation were captured in the 1-Hz aircraft observations, inferred from the distributions of relative humidity in the nucleation phase. Using linear regressions to quantify the correlations between cirrus microphysical properties and aerosol number concentrations, we found that ice water content (IWC) and ice crystal number concentration (Ni) show strong positive correlations with larger aerosols (> 500 nm) in the nucleation phase, indicating strong contributions of heterogeneous nucleation when ice crystals first start to nucleate. For the later growth phase, IWC and Ni show similar positive correlations with larger and smaller (i.e., > 100 nm) aerosols, possibly due to fewer remaining ice nucleating particles in the later growth phase that allows more homogeneous nucleation to occur. Both 200-m and 100-km observations were compared with the nudged simulations from the National Center for Atmospheric Research (NCAR) Community Atmosphere Model version 6 (CAM6). Simulated aerosol indirect effects are weaker than the observations for both larger and smaller aerosols. Observations show stronger aerosol indirect effects (i.e., positive correlations between IWC, Ni and Na) in the Southern Hemisphere (SH) compared with the Northern Hemisphere (NH), while the simulations show negative correlations in the SH. The simulations underestimate IWC by a factor of 3 – 30 in the early/later growth phase, indicating that the low bias of simulated IWC was due to insufficient ice particle growth. Such hypothesis is consistent with the model biases of lower frequencies of ice supersaturation and lower vertical velocity standard deviation in the early/later growth phases. Overall, these findings show that aircraft observations can capture the competitions between heterogeneous and homogeneous nucleation, and their contributions vary as cirrus clouds evolve. Future model development is also recommended to evaluate and improve the representation of water vapor and vertical velocity on the sub-grid scale to resolve the insufficient ice particle growth. 
    more » « less
  4. Abstract. Some biological particles, such as Snomax, are very active ice nucleating particles, inducing heterogeneous freezing in supercooled water at temperatures above −15 and up to −2 °C. Despite their exceptional freezing abilities, large uncertainties remain regarding the atmospheric abundance of biological ice nucleating particles, and their contribution to atmospheric ice nucleation. It has been suggested that small biological ice nucleating macromolecules or fragments can be carried on the surfaces of dust and other atmospheric particles. This could combine the atmospheric abundance of dust particles with the ice nucleating strength of biological material to create strongly enhanced and abundant ice nucleating surfaces in the atmosphere, with significant implications for the budget and distribution of atmospheric ice nucleating particles, and their consequent effects on cloud microphysics and mixed-phase clouds. The new critical surface area g framework that was developed by Beydoun et al. (2016) is extended to produce a heterogeneous ice nucleation mixing model that can predict the freezing behavior of multicomponent particle surfaces immersed in droplets. The model successfully predicts the immersion freezing properties of droplets containing Snomax bacterial particles across a mass concentration range of 7 orders of magnitude, by treating Snomax as comprised of two distinct distributions of heterogeneous ice nucleating activity. Furthermore, the model successfully predicts the immersion freezing behavior of a low-concentration mixture of Snomax and illite mineral particles, a proxy for the biological material–dust (bio-dust) mixtures observed in atmospheric aerosols. It is shown that even at very low Snomax concentrations in the mixture, droplet freezing at higher temperatures is still determined solely by the second less active and more abundant distribution of heterogeneous ice nucleating activity of Snomax, while freezing at lower temperatures is determined solely by the heterogeneous ice nucleating activity of pure illite. This demonstrates that in this proxy system, biological ice nucleating particles do not compromise their ice nucleating activity upon mixing with dust and no new range of intermediary freezing temperatures associated with the mixture of ice nucleating particles of differing activities is produced. The study is the first to directly examine the freezing behavior of a mixture of Snomax and illite and presents the first multicomponent ice nucleation model experimentally evaluated using a wide range of ice nucleating particle concentration mixtures in droplets. 
    more » « less
  5. Carbon nanotube (CNT)/epoxy nanocomposites have a great potential of possessing many advanced properties. However, the homogenization of CNT dispersion is still a great challenge in the research field of nanocomposites. This study applied a novel dispersion agent, carboxymethyl cellulose (CMC), to functionalize CNTs and improve CNT dispersion in epoxy. The effectiveness of the CMC functionalization was compared with mechanical mixing and a commonly used surfactant, sodium dodecylbenzene sulfonate (NaDDBS), regarding dispersion, mechanical and corrosion properties of CNT/epoxy nanocomposites with three different CNT concentrations (0.1%, 0.3% and 0.5%). The experimental results of Raman spectroscopy, particle size analysis and transmission electron microscopy showed that CMC functionalized CNTs reduced CNT cluster sizes more efficiently than NaDDBS functionalized and mechanically mixed CNTs, indicating a better CNT dispersion. The peak particle size of CMC functionalized CNTs reduced as much as 54% (0.1% CNT concentration) and 16% (0.3% CNT concentration), compared to mechanical mixed and NaDDBS functionalized CNTs. Because of the better dispersion, it was found by compressive tests that CNT/epoxy nanocomposites with CMC functionalization resulted in 189% and 66% higher compressive strength, 224% and 50% higher modulus of elasticity than those with mechanical mixing and NaDDBS functionalization respectively (0.1% CNT cencentration). In addition, electrochemical corrosion tests also showed that CNT/epoxy nanocomposites with CMC functionalization achieved lowest corrosion rate (0.214 mpy), the highest corrosion resistance (201.031 Ω·cm2), and the lowest porosity density (0.011%). 
    more » « less