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.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Polymer–Plasticizer Coatings for BTEX Detection Using Quartz Crystal Microbalance
Sensing films based on polymer–plasticizer coatings have been developed to detect volatile organic compounds (VOCs) in the atmosphere at low concentrations (ppm) using quartz crystal microbalances (QCMs). Of particular interest in this work are the VOCs benzene, ethylbenzene, and toluene which, along with xylene, are collectively referred to as BTEX. The combinations of four glassy polymers with five plasticizers were studied as prospective sensor films for this application, with PEMA-DINCH (5%) and PEMA-DIOA (5%) demonstrating optimal performance. This work shows how the sensitivity and selectivity of a glassy polymer film for BTEX detection can be altered by adding a precise amount and type of plasticizer. To quantify the film saturation dynamics and model the absorption of BTEX analyte molecules into the bulk of the sensing film, a diffusion study was performed in which the frequency–time curve obtained via QCM was correlated with gas-phase analyte composition and the infinite dilution partition coefficients of each constituent. The model was able to quantify the respective concentrations of each analyte from binary and ternary mixtures based on the difference in response time (τ) values using a single polymer–plasticizer film as opposed to the traditional approach of using a sensor array. This work presents a set of polymer–plasticizer coatings that can be used for detecting and quantifying the BTEX in air, and discusses the selection of an optimum film based on τ, infinite dilution partition coefficients, and stability over a period of time.  more » « less
Award ID(s):
1640668
PAR ID:
10316050
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Sensors
Volume:
21
Issue:
16
ISSN:
1424-8220
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; (, Atmospheric Measurement Techniques)
    Abstract. Previous studies have demonstrated volatility-dependent absorption of gas-phase volatile organic compounds (VOCs) to Teflon and other polymers. Polymer–VOC interactions are relevant for atmospheric chemistry sampling, as gas–wall partitioning in polymer tubing can cause delays and biases during measurements. They are also relevant to the study of indoor chemistry, where polymer-based materials are abundant (e.g., carpets and paints). In this work, we quantify the absorptive capacities of multiple tubing materials, including four nonconductive polymers (important for gas sampling and indoor air quality), four electrically conductive polymers and two commercial steel coatings (for gas and particle sampling). We compare their performance to previously characterized materials. To quantify the absorptive capacities, we expose the tubing to a series of ketones in the volatility range 104–109 µg m−3 and monitor transmission. For slow-diffusion polymers (e.g., perfluoroalkoxy alkane (PFA) Teflon and nylon), absorption is limited to a thin surface layer, and a single-layer absorption model can fit the data well. For fast-diffusion polymers (e.g., polyethylene and conductive silicone), a larger depth of the polymer is available for diffusion, and a multilayer absorption model is needed. The multilayer model allows fitting solid-phase diffusion coefficients for different materials, which range from 4×10-9 to 4×10-7 cm2 s−1. These diffusion coefficients are ∼ 8 orders of magnitude larger than literature values for fluorinated ethylene propylene (FEP) Teflon film. This enormous difference explains the differences in VOC absorption measured here. We fit an equivalent absorptive mass (CW, µg m−3) for each absorptive material. We found PFA to be the least absorptive, with CW ∼ 105 µg m−3, and conductive silicone to be the most absorptive, with CW ∼ 1013 µg m−3. PFA transmits VOCs easily and intermediate-volatility species (IVOCs) with quantifiable delays. In contrast, conductive silicone tubing transmits only the most volatile VOCs, denuding all lower-volatility species. Semi-volatile species (SVOCs) are very difficult to sample quantitatively through any tubing material. We demonstrate a system combining several slow- and fast-diffusion tubing materials that can be used to separate a mixture of VOCs into volatility classes. New conductive silicone tubing contaminated the gas stream with siloxanes, but this effect was reduced 10 000-fold for aged tubing, while maintaining the same absorptive properties. SilcoNert (tested in this work) and Silonite (tested in previous work) steel coatings showed gas transmission that was almost as good as PFA, but since they undergo adsorption, their delay times may be humidity- and concentration-dependent. 
    more » « less
  2. ; ; ; ; ; ; ; ; (, ACS Applied Polymer Materials)
    With the growing number of applications for thin polymer films (e.g., corrosion-resistant coatings, photovoltaics, and optoelectronics), there is an urgent need to develop or advance cost-effective, versatile, and high-throughput manufacturing processes to produce thin polymer films and coatings with controllable properties (e.g., morphology, composition). In this work, we present a simple, cost-effective, and scalable approach: the air-assisted electrospray method for thin film coating. We systematically investigate its capabilities for producing coatings with a wide range of surface morphologies, its compatibility with three-dimensional substrates, and the fundamental understanding of the process. Through systematic control of concentration, needle configuration, and polymer selection, we demonstrate the ability to produce coating morphologies with diverse structural characteristics and excellent reproducibility. Notably, the introduction of air assistance through a coaxial needle greatly enlarges the range of achievable morphologies, particularly at lower concentrations. We also found that the position of the airflow relative to the solution is critical for determining the polymer film properties. Furthermore, we demonstrate its broad application potential in the fabrication of binderless electrodes for sodium-ion batteries. 
    more » « less
  3. ; ; ; (, Sensors)
    Herein, we examine two sensing schemes for detection and discrimination of chlorinated volatile organic compounds (VOCs). In this work, phosphonium ionic liquids (ILs) were synthesized and vapor sensing properties examined and compared to phosphonium IL-polymer composites. Pure IL sensors were used to develop a QCM-based multisensory array (MSA), while IL-polymer composites were used to develop an MSA and virtual sensor arrays (VSAs). It was found that by employing the composite MSA, five chlorinated VOCs were accurately discriminated at 95.56%, which was an increase in accuracy as compared to pure ILs MSA (84.45%). Data acquired with two out of three VSAs allowed discrimination of chlorinated VOCs with 100% accuracy. These studies have provided greater insight into the benefits of incorporating polymers in coating materials for enhanced discrimination accuracies of QCM-based sensor arrays. To the best of our knowledge, this is the first report of a QCM-based VSA for discrimination of closely related chlorinated VOCs. 
    more » « less
  4. ; ; ; ; (, Journal of Polymer Science)
    Abstract We developed the dynamic assembly of the hydrogen‐bonded multilayers of (poly(N‐vinylpyrrolidone/poly(methacrylic acid)) (PVPON/PMAA)) and compared their properties to the static multilayers. We found that dynamic multilayers, wherein a planar substrate is shaken during polymer adsorption, leads to a 15‐time faster deposition of the planar coatings. The thicknesses and roughness of the dynamic coatings were found to be ⁓30% larger than those of static (no shaking) multilayer films as measured by spectroscopic ellipsometry and atomic force microscopy. We examined the film growth, mechanical properties, wettability, hydration, and pH stability of the planar static and dynamic multilayers and demonstrated that these properties were insignificantly affected by the assembly mode. Both static and dynamic coatings produced microporous films when exposed to pH = 5.9, close to the film critical dissolution pH = 6. We discovered that during the release of the multilayer films into a solution to produce free‐standing films either as planar membranes or multilayer capsule shells, the molecular chain rearrangements result in the decreased roughness for both static and dynamic multilayers and lead to a decreased thickness of the dynamic multilayers. Our findings can help develop a rapid synthesis of thicker nanostructured polymer coatings for sensing and controlled delivery applications. 
    more » « less
  5. ; ; ; ; ; ; ; (, Biosensors and Bioelectronics)
    Electrically conductive, genetically tunable, pilin-based protein nanowires (ePNs) expressed in Escherichia coli grown on the biodiesel byproduct glycerol are a sustainable electronic material. They were previously shown to effectively function as sensing components for volatile analytes when deployed as thin films in electronic devices. However, thin-film devices are not suitable for analyzing components dissolved in water. To evaluate the possibility of fabricating a water-stable ePN matrix, ePNs purified from cells were mixed with polyvinyl butyral (PVB) to produce a transparent, electrically conductive, water-stable composite. ePN/PVB composite conductivity was tuned by changing the concentration of ePNs in the composite or genetically tailoring ePNs for different conductivities. Devices with an ePN/PVB sensing component rapidly responded in a linear fashion to changes in concentrations of dissolved ammonia or acetate. Genetically modifying nanowires to display an analyte-binding peptide on the ePN outer surface that was specific for ammonia or acetate increased sensing sensitivity and specificity. Composites comprised of whole cells of E. coli expressing ePNs and PVB were also electrically conductive. They functioned as sensing components whose sensitivity could also be tuned with the expression of ePNs displaying specific analyte-binding peptides. This approach avoids the laborious and time-consuming purification of protein nanowires from cells. The simplicity of sustainably fabricating an electronic sensing component with ePN-expressing E. coli mixed with a polymer, coupled with the potential of exquisitely tuning sensing specificity with facile ‘plug and play’ nanowire design, demonstrates the possibility of simply and inexpensively producing sensing devices for detecting a broad range of analytes. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email