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15 pages, 2335 KiB  
Article
Looping Flexible Fluoropolymer Microcapillary Film Extends Analysis Times for Vertical Microfluidic Blood Testing
by Rüya Meltem Sarıyer, Kirandeep K. Gill, Sarah H. Needs, Nuno M. Reis, Chris I. Jones and Alexander Daniel Edwards
Sensors 2024, 24(18), 5870; https://doi.org/10.3390/s24185870 - 10 Sep 2024
Viewed by 275
Abstract
The microfluidic measurement of capillary flow can be used to evaluate the response of biological samples to stimulation, where distance and velocity are altered. Melt-extruded multi-bored microfluidic capillaries allow for high-throughput testing with low device cost, but simple devices may limit control over [...] Read more.
The microfluidic measurement of capillary flow can be used to evaluate the response of biological samples to stimulation, where distance and velocity are altered. Melt-extruded multi-bored microfluidic capillaries allow for high-throughput testing with low device cost, but simple devices may limit control over sample flow when compared to the more complex “lab-on-a-chip” devices produced using advanced microfluidic fabrication methods. Previously, we measured the dynamics of global haemostasis stimulated by thrombin by dipping straight vertical microcapillaries into blood, but only the most rapid response could be monitored, as flow slowed significantly within 30 s. Here, we show an innovative method to extend both the stimulation process and flow measurement time without increasing the cost of the device by adding simple loops to the flexible extruded device. The loops enable longer time-scale measurements by increasing resistance to flow, thereby reducing the dependence on high stimulus concentrations for rapid reactions. The instantaneous velocity and equilibrium heights of straight and looped vertical microcapillary films were assessed with water, plasma and whole blood, showing that the loops create additional frictional resistances, reduce flow velocity and prolong residence times for increased time scales of the stimulation process. A modified pressure balance model was used to capture flow dynamics with the added loop. Looped devices loaded with thrombin and collagen showed an improved detection of blood stimulation responses even with lower stimulus concentrations, compared to straight vertical capillaries. Thrombin-activated blood samples in straight capillaries provided a maximum measurement zone of only 4 mm, while the looped design significantly increased this to 11 mm for much longer time scale measurements. Our results suggest that extending stimulation times can be achieved without complex microfluidic fabrication methods, potentially improving concentration–response blood stimulation assays, and may enhance the accuracy and reliability. We conclude adding a loop to low-cost extruded microfluidic devices may bring microfluidic devices closer to delivering on their promise of widespread, decentralized low-cost evaluation of blood response to stimulation in both research and clinical settings. Full article
(This article belongs to the Special Issue Biomedical Sensors Based on Microfluidics)
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<p>The loop design provides a way of increasing the measurement range by controlling the stimulation time. (<b>a</b>) Concept of capillary rise in “dip-and-test” microfluidic straight vertical dipsticks to measure blood function. (<b>b</b>) Vertical capillary rise with added loop concept with front and side view. (<b>c</b>) The dip-stick tests work by allowing blood samples to flow up vertically into ~200-micron straight channels where the blood mixes with stimuli. When a simple loop is added to the vertical dipstick, blood flows vertically upwards, but then around a loop, and while in that loop it begins to be stimulated. (<b>d</b>) The vertical flow in straight channels takes only a few seconds before slowing down. With the addition of a loop, this rapid flow continues for &gt;30 s or so. (<b>e</b>) A representation of capillary rise in height and length over time for straight, loop- and double-loop-added dipsticks. Data indicates the mean of 10 replicate capillaries where error bars indicate ± SD from a single donor; similar results were observed in 2 replicate experiments with different donors. (<b>f</b>) In loop dipsticks, the blood rises over a greater distance due to the added length of the loop. Straight dipsticks increase by about 10 mm after 30 s, while looped dipsticks achieve around 30 mm within the same time.</p>
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<p>Adding loops to the straight vertical strips creates additional frictional resistances (<math display="inline"><semantics> <mrow> <mo>∆</mo> <mi>P</mi> <mi>F</mi> </mrow> </semantics></math>). (<b>a</b>) <math display="inline"><semantics> <mrow> <msub> <mrow> <mo>∆</mo> <mi>P</mi> </mrow> <mrow> <mi>F</mi> <mn>1</mn> </mrow> </msub> </mrow> </semantics></math> represents the pressure difference driving the flow, while <math display="inline"><semantics> <mrow> <msub> <mrow> <mo>∆</mo> <mi>P</mi> </mrow> <mrow> <mi>F</mi> <mn>2</mn> </mrow> </msub> </mrow> </semantics></math> and <math display="inline"><semantics> <mrow> <msub> <mrow> <mo>∆</mo> <mi>P</mi> </mrow> <mrow> <mi>F</mi> <mn>2</mn> </mrow> </msub> <mo>+</mo> <msub> <mrow> <mo>∆</mo> <mi>P</mi> </mrow> <mrow> <mi>F</mi> <mn>3</mn> </mrow> </msub> </mrow> </semantics></math> represent the additional pressure differences due to the loops. (<b>b</b>) The graph shows how the instantaneous superficial fluid velocity <math display="inline"><semantics> <mrow> <mi>d</mi> <mi>H</mi> <mo>/</mo> <mi>d</mi> <mi>t</mi> </mrow> </semantics></math> changes with the reciprocal <math display="inline"><semantics> <mrow> <mi>H</mi> <mo>(</mo> <mi>t</mi> <mo>)</mo> </mrow> </semantics></math> for each fluid. The experimental data points are plotted along with the model predictions calculated from the transient pressure balance. The dynamic flows observed for pure water, PRP and WB in straight strips fit our model. Data were collected from 10 replicate capillaries, with error bars representing ± SD from a single donor; consistent results were observed across 2 replicate experiments with different donors. (<b>c</b>) Graphs show experimental data points and corresponding model predictions for straight, single-loop and double-loop configurations. Adding loops reduces the flow rate, which leads to longer residence times. The differences in flow rate become more pronounced with different fluid viscosities. Mean of 10 replicate capillaries are shown in the chart, with similar results across 2 independent experiments (N = 2).</p>
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<p>The capillary rise is unaffected by the loop, and impact of stimulation with thrombin and collagen can be measured. (<b>a</b>) Demonstration of the capillary rise of water, buffer and blood components in straight, loop- and double-loop-added dipsticks after 15 s. (<b>b</b>) An image of the strips before reaching equilibrium height. Strips of different sizes were used. (<b>c</b>) After 10 min, the equilibrium heights reached by water, plasma, and blood in the dipsticks with straight, loop, and double-loop configurations showed nearly the same values. Data indicates 10 replicate capillaries where error bars indicate ± SD from a single donor. (<b>d</b>) At the end of the 2 min experiment, stimulation was observed in straight and loop-added dipsticks loaded with thrombin (loaded with 0, 5, 15, 50, 150 and 300 U mL<sup>−1</sup>). Since blood at concentrations of 50 U mL<sup>−1</sup> and above could not pass through the loop within the 2 min time frame, these concentrations are not included in the calculations. The images provided are representative examples, with similar results observed across four different donors (N = 4). (<b>e</b>) Stimulation was observed in straight and loop-added dipsticks loaded with collagen (loaded with 0, 50, 158 and 500 mg mL<sup>−1</sup>). The images are representative examples of three replicate collagen stimulation experiments (N = 3).</p>
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16 pages, 2755 KiB  
Article
Microplastics in the Mississippi River System during Flash Drought Conditions
by Kendall Wontor, Boluwatife S. Olubusoye and James V. Cizdziel
Environments 2024, 11(7), 141; https://doi.org/10.3390/environments11070141 - 3 Jul 2024
Viewed by 875
Abstract
The Mississippi River System is of great ecological and economic importance, making it crucial to monitor contaminants within it. While nutrient pollution is well studied, there are little data on microplastics (MPs) in the Mississippi River System (MSRS), especially during drought conditions. Herein, [...] Read more.
The Mississippi River System is of great ecological and economic importance, making it crucial to monitor contaminants within it. While nutrient pollution is well studied, there are little data on microplastics (MPs) in the Mississippi River System (MSRS), especially during drought conditions. Herein, we characterize MP pollution from seven sites across the MSRS during both flash drought and non-drought periods using FTIR microspectroscopy (µ-FTIR). Additionally, we evaluate the impact of multiple water level conditions on MP polymer composition across five time points at a single sampling site. Of all MPs identified, polyethylene terephthalate (PET, 22%), resin (17%), and polyethylene (PE, 10%) were the most abundant polymers. Average concentrations ranged from 16 to 381 MPs/L across seven sites, with no significant difference in concentration between conditions. Irregular particles were the most common morphology, with most MPs falling in the lowest size range measured (30–100 μm). Drought condition had a significant (p < 0.001) impact on polymer composition, and polymers most strongly correlated with flash drought were mostly fluoropolymers. For the single sampling site, concentrations differed, but not significantly, across the five timepoints. These results demonstrate the complex relationship between MP concentration and drought condition, and also highlight the importance of fully characterizing MPs in environmental studies. Full article
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<p>Percent area of the United States Army Corps of Engineers’ Memphis District in US Drought Monitor Categories [<a href="#B20-environments-11-00141" class="html-bibr">20</a>]. Categories shown include normal or wet conditions (none, dark blue), abnormally dry conditions that have not yet met the threshold for a drought (D0, light blue), moderate drought (D1, peach), severe drought (D2, light red), extreme drought (D3, dark red), and exceptional drought (D4, conditions not present).</p>
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<p>Sampling locations within the Mississippi River System. Sites include the Mississippi River (black circles) and tributary rivers (open circles). A description of the sampling sites is given in <a href="#environments-11-00141-t001" class="html-table">Table 1</a>.</p>
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<p>Microplastics tagged for FTIR analysis and representative spectra. Optical image of a silicon filter showing the distribution of particles to be tagged for analysis (<b>left</b>). Database spectrum of PET (<b>top</b>), along with two particles of HQI values 683 (<b>middle</b>) and 424 (<b>bottom</b>). Characteristic peaks of PET are depicted by black dotted lines at 1721, 1245, and 110 cm<sup>−1</sup> [<a href="#B27-environments-11-00141" class="html-bibr">27</a>] with additional PET peaks shown in gray at 1409, 967, and 869 cm<sup>−1</sup> [<a href="#B28-environments-11-00141" class="html-bibr">28</a>].</p>
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<p>Polymer composition of total microplastics identified in this study (<span class="html-italic">n</span> = 6209). For readability, only the top 10 polymers have been shown. See <a href="#app1-environments-11-00141" class="html-app">supplemental information for a list of the other MPs identified (Figure S1)</a>.</p>
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<p>Physical characteristics of MPs from flash drought and normal sample sets, including morphology (<b>top left</b>), size distribution (<b>bottom left</b>) and the distribution of MP morphologies by size (<b>right</b>, outliers above 1500 µm excluded). Data exclude one sample from site 6. (<span class="html-italic">n</span> = 6131).</p>
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<p>Average MP concentrations by sampling site across both flash drought and normal flow conditions. Abbreviation of river name listed in parenthesis after site name. Error bars represent one standard error.</p>
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<p>Average microplastics concentration (MPs/L) by condition at Memphis, TN (Site 7). Error bars represent one standard error.</p>
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16 pages, 5393 KiB  
Article
Direct Defluorination and Amination of Polytetrafluoroethylene and Other Fluoropolymers by Lithium Alkylamides
by Guillaume Herlem, Yaelle Roina, Mathieu Fregnaux, Anne-Marie Gonçalves, Hélène Cattey, Fabien Picaud and Frédéric Auber
Molecules 2024, 29(13), 3045; https://doi.org/10.3390/molecules29133045 - 26 Jun 2024
Viewed by 988
Abstract
Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and [...] Read more.
Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and some fluoropolymers such as polyvinylidene fluoride (PVDF) and Nafion by lithium alkylamide salts. Synthesizing these reactants extemporaneously between lithium metal and an aliphatic primary di- or triamine that also serves as a solvent leads to the rapid nucleophilic substitution of fluoride by an alkylamide moiety when in contact with the fluoropolymer. Moreover, lithium alkylamides dissolved in suitable solvents other than amines can react with fluoropolymers. This highly efficient one-pot process opens the way for further surface or bulk modification if needed, providing an easy, inexpensive, and fast experiment protocol on large scales. Full article
(This article belongs to the Section Macromolecular Chemistry)
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<p>Synthesis of lithium alkylamides, their reactive centers, and the crystal structure of LiEDA. The XRD structure of (<b>a</b>) LiEDA synthesized from the fast reaction between Li and EDA in stoichiometric proportions. The powder XRD of (<b>b</b>) LiDETA and (<b>c</b>) LiDAP. (<b>d</b>) The synthesis scheme of LiEDA, LiDETA, and LiDAP by the reaction of lithium with EDA, DETA, or DAP, respectively. Isosurface maps of dual descriptors (Δ<span class="html-italic">f</span>) for (<b>e</b>) LiEDA, (<b>f</b>) LiDETA, (<b>g</b>) LiDAP, and (<b>h</b>) PTFE. Positive and negative regions of the dual descriptor Δ<span class="html-italic">f</span> are represented as blue and red colors, respectively.</p>
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<p>SEM images of (<b>a</b>) a PTFE surface modified by (<b>b</b>) LiEDA, (<b>c</b>) LiDETA, (<b>d</b>) LiDAP. (<b>e</b>) PTFE cross-sections (<b>f</b>) modified by LiEDA. (<b>g</b>) Pristine Nafion modified by (<b>h</b>) LiEDA and (<b>i</b>) LiDETA.</p>
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<p>Surface analysis by XPS. XPS spectra of PTFE modified by LiEDA for (<b>a</b>) C1s, (<b>b</b>) N1s, and (<b>c</b>) F1s. XPS spectra of PVDF modified by LiDETA for (<b>d</b>) C1s, (<b>e</b>) N1s, and (<b>f</b>) F1s. XPS spectra of Nafion modified by LiEDA for (<b>g</b>) C1s, (<b>h</b>) N1s, and (<b>i</b>) F1s.</p>
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<p>Vibrational analysis by IR-ATR and Raman spectroscopies of PTFE, PVDF, and Nafion modified by lithium alkylamides. (<b>a</b>) IR-ATR spectra of pristine PTFE and its chemical modifications by LiEDA and LiDETA. (<b>b</b>) IR-ATR spectra of pristine Nafion and its chemical modifications by LiEDA and LiDETA. (<b>c</b>) IR-ATR spectra of pristine PVDF membrane and its chemical modifications by LiEDA, LiDETA, and LiDAP. (<b>d</b>) Raman spectra of pristine PTFE and PTFE and its chemical modifications by LiEDA and LiDETA as well as EDA solvent (excitation 785 nm).</p>
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<p>Surface free energy and corresponding contact angle values (in blue). The error bars are calculated with the propagation of uncertainty using first-order Taylor expansion applied to Fowkes’ theory formulas [<a href="#B11-molecules-29-03045" class="html-bibr">11</a>].</p>
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<p>Energy dispersive spectra of (<b>a</b>) bare PTFE, (<b>b</b>) PTFE modified by LiEDA, and (<b>c</b>) PTFE modified by LiDETA.</p>
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<p>EDX mapping of C, O, and F elements of bare PTFE.</p>
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<p>EDS mapping of C, N and O elements of the surface of PTFE modified by LiEDA.</p>
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<p>EDX mapping of C, N, O, and F elements of PTFE modified by LiDETA.</p>
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<p>Suggested reaction mechanism between a fluoropolymer and the lithium alkylamide.</p>
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13 pages, 3340 KiB  
Article
Stable N-Type Single-Walled Carbon Nanotube/Mesh Sheets by Cationic Surfactant Doping and Fluoropolymer Coating for Flexible Thermoelectric Generators
by Takuya Amezawa and Masayuki Takashiri
Coatings 2024, 14(7), 794; https://doi.org/10.3390/coatings14070794 - 26 Jun 2024
Viewed by 1076
Abstract
Single-walled carbon nanotubes (SWCNTs) offer promise as materials for thermoelectric generators (TEGs) due to their flexibility, durability, and non-toxic nature. However, a key barrier to their application lies in their high thermal conductivity, which hampers the generation of temperature differences in TEGs. To [...] Read more.
Single-walled carbon nanotubes (SWCNTs) offer promise as materials for thermoelectric generators (TEGs) due to their flexibility, durability, and non-toxic nature. However, a key barrier to their application lies in their high thermal conductivity, which hampers the generation of temperature differences in TEGs. To address this challenge, we explored a method of enhancing the heat dissipation of SWCNT-based TEGs by coating SWCNT layers onto polymer mesh sheets. During TEG fabrication, achieving stable n-type SWCNT/mesh sheets proved considerably more challenging than their p-type counterparts. This difficulty stemmed from the inferior dispersibility of the n-type SWCNT ink compared to the p-type SWCNT ink. To produce n-type SWCNT/mesh sheets, we initially prepared p-type SWCNT/mesh sheets using p-type SWCNT ink, subsequently doping them with a cationic surfactant solution to induce n-type characteristics. To stabilize the n-type thermoelectric properties in SWCNT/mesh sheets, we applied a fluoropolymer coating to the SWCNT surfaces, mitigating the adsorption of oxygen molecules. This approach yielded n-type SWCNT/mesh sheets capable of long-term maintenance. Furthermore, flexible TEGs fabricated using both p- and n-type SWCNT/mesh sheets demonstrated an output voltage of 15 mV, which can operate IoT sensors using the latest booster circuits, and a maximum power of 100 nW at a temperature difference of 71 K. Full article
(This article belongs to the Special Issue Thermoelectric Materials for Sustainable Applications)
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<p>Manufacturing process of SWCNT/mesh sheets.</p>
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<p>SEM images of SWCNT/mesh sheets at each stage of the manufacturing process: (<b>a</b>) PPS mesh sheet, (<b>b</b>) Sample A-1, (<b>c</b>) Sample A-2, (<b>d</b>) Sample B-1, (<b>e</b>) Sample B-2, (<b>f</b>) Sample C-1, and (<b>g</b>) Sample C-2.</p>
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<p>XPS spectra of SWCNT/mesh sheets with fluoropolymer spraying: (<b>a</b>) entire XPS spectra, (<b>b</b>) C1s spectra, (<b>c</b>) F1s spectra, and (<b>d</b>) O1s spectra.</p>
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<p>In-plane thermoelectric properties of SWCNT/mesh sheets measured at 25 °C: (<b>a</b>) Seebeck coefficient, (<b>b</b>) electrical conductivity and (<b>c</b>) power factor.</p>
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<p>Changes in Seebeck coefficients of SWCNT/mesh sheets over time with and without fluoropolymer coating.</p>
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<p>Manufacturing process and measurement procedure of the FTEG with p- and n-type SWCNT/mesh sheets.</p>
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<p>Power generation performance of FTEGs with p- and n-type SWCNT/mesh sheets: (<b>a</b>) single SWCNT dip and (<b>b</b>) double SWCNT dip.</p>
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11 pages, 1561 KiB  
Article
Occurrence and Risk Assessment of Perfluoroalkyl Substances in Surface Water of Hefei City, Southeast China
by Yu Zhang, Chuanjun Jiang, Liangpu Zhang, Hua Cheng and Ning Wang
Water 2024, 16(9), 1245; https://doi.org/10.3390/w16091245 - 26 Apr 2024
Viewed by 837
Abstract
In this work, the spatial distribution, potential sources, and risk assessment of perfluoroalkyl substances (PFASs) were investigated at 22 surface water sampling sites in Hefei City. The study encompassed 11 distinct types of PFASs, which included 7 perfluoroalkyl carboxylic acids (PFCAs) and 4 [...] Read more.
In this work, the spatial distribution, potential sources, and risk assessment of perfluoroalkyl substances (PFASs) were investigated at 22 surface water sampling sites in Hefei City. The study encompassed 11 distinct types of PFASs, which included 7 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonic acids (PFSAs). The findings indicated that the overall concentration of PFASs varied between 12.96 to 545.50 ng/L, with perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS), perfluorobutyric acid (PFBA), and perfluorohexanoic acid (PFHxA) being the most prevalent, contributing to an average of 71% of the total PFASs concentration. Principal component analysis (PCA) elucidated the primary sources of PFASs, which included industrial emissions, fluoropolymer production and treatment, textile processing, and the impact of the electroplating industry. Employing the risk quotient (RQ) method facilitated the assessment of ecological risks associated with PFASs in surface water within the study area, suggesting that the current concentrations of PFASs in Hefei’s surface water pose a relatively low ecological risk. However, the long-term ecological effects of PFASs cannot be overlooked due to their potential for long-range transport and the cumulative nature of biological food chains. Full article
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<p>Distribution of sampling sites.</p>
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<p>Compositions and distribution of individual PFASs.</p>
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<p>Distribution of individual PFASs at each site (ng/L).</p>
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<p>Spearman correlation coefficients between the concentrations of PFASs.</p>
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<p>Ratio of PFOS/PFOA, PFOA/PFNA, and PFHpA/PFOA at each site.</p>
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9 pages, 5929 KiB  
Communication
Efficient Separation of Methanol Single-Micron Droplets by Tailing Phenomenon Using a PDMS Microfluidic Device
by Daiki Tanaka, Shengqi Zheng, Masahiro Furuya, Masashi Kobayashi, Hiroyuki Fujita, Takashiro Akitsu, Tetsushi Sekiguchi and Shuichi Shoji
Molecules 2024, 29(9), 1949; https://doi.org/10.3390/molecules29091949 - 24 Apr 2024
Viewed by 699
Abstract
Microdroplet-based fluidic systems have the advantages of small size, short diffusion time, and no cross-contamination; consequently, droplets often provide a fast and precise reaction environment as well as an analytical environment for individual molecules. In order to handle diverse reactions, we developed a [...] Read more.
Microdroplet-based fluidic systems have the advantages of small size, short diffusion time, and no cross-contamination; consequently, droplets often provide a fast and precise reaction environment as well as an analytical environment for individual molecules. In order to handle diverse reactions, we developed a method to create organic single-micron droplets (S-MDs) smaller than 5 μm in diameter dispersed in silicone oil without surfactant. The S-MD generation microflow device consists of a mother droplet (MoD) generator and a tapered separation channel featuring multiple side channels. The tapered channel enhanced the shear forces to form tails from the MoDs, causing them to break up. Surface treatment with the fluoropolymer CYTOP protected PDMS fluid devices from organic fluids. The tailing separation of methanol droplets was accomplished without the use of surfactants. The generation of tiny organic droplets may offer new insights into chemical separation and help study the scaling effects of various chemical reactions. Full article
(This article belongs to the Section Nanochemistry)
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<p>Scenes of three-dimensional CFD simulation in T-junction [<a href="#B28-molecules-29-01949" class="html-bibr">28</a>]: (<b>a</b>) Contact angle of 30 degrees. (<b>b</b>) Contact angle of 150 degrees.</p>
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<p>Optical microscopy images showing S-MD formation.</p>
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<p>Methanol S-MD diameter under different carrier flow rates.</p>
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<p>Relationship between the diameter of the generated S-MDs and continuous flow velocity.</p>
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<p>Variation in S-MD features with flow velocity.</p>
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<p>Schematic diagram and dimensions of the device. (<b>A</b>) Device design. (<b>B</b>) Comparison of the flow paths with and without added surfactant.</p>
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<p>Flow charts showing the (<b>a</b>) device fabrication and (<b>b</b>) surface modification processes.</p>
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<p>Microfluidic device appearance and experimental system. (<b>a</b>) PDMS microfluidic device. (<b>b</b>) Fluid experiment setup.</p>
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19 pages, 5861 KiB  
Article
Fluorocarbon Plasma-Polymerized Layer Increases the Release Time of Silver Ions and the Antibacterial Activity of Silver-Based Coatings
by Linda Bonilla-Gameros, Pascale Chevallier, Xavier Delvaux, L. Astrid Yáñez-Hernández, Laurent Houssiau, Xavier Minne, Vanessa P. Houde, Andranik Sarkissian and Diego Mantovani
Nanomaterials 2024, 14(7), 609; https://doi.org/10.3390/nano14070609 - 29 Mar 2024
Viewed by 977
Abstract
Silver-based antibacterial coatings limit the spread of hospital-acquired infections. Indeed, the use of silver and silver oxide nanoparticles (Ag and AgO NPs) incorporated in amorphous hydrogenated carbon (a-C:H) as a matrix demonstrates a promising approach to reduce microbial contamination on environmental surfaces. However, [...] Read more.
Silver-based antibacterial coatings limit the spread of hospital-acquired infections. Indeed, the use of silver and silver oxide nanoparticles (Ag and AgO NPs) incorporated in amorphous hydrogenated carbon (a-C:H) as a matrix demonstrates a promising approach to reduce microbial contamination on environmental surfaces. However, its success as an antibacterial coating hinges on the control of Ag+ release. In this sense, if a continuous release is required, an additional barrier is needed to extend the release time of Ag+. Thus, this research investigated the use of a plasma fluoropolymer (CFx) as an additional top layer to elongate Ag+ release and increase the antibacterial activity due to its high hydrophobic nature. Herein, a porous CFx film was deposited on a-C:H containing Ag and AgO NPs using pulsed afterglow low pressure plasma polymerization. The chemical composition, surface wettability and morphology, release profile, and antibacterial activity were analyzed. Overall, the combination of a-C:H:Ag (12.1 at. % of Ag) and CFx film (120.0°, F/C = 0.8) successfully inactivated 88% of E. coli and delayed biofilm formation after 12 h. Thus, using a hybrid approach composed of Ag NPs and a hydrophobic polymeric layer, it was possible to increase the overall antibacterial activity of the coating. Full article
(This article belongs to the Section Synthesis, Interfaces and Nanostructures)
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<p>Chemical composition of the uncoated and CF<sub>x</sub>-coated a-C:H samples with different studied conditions. (<b>a</b>) XPS survey results and (<b>b</b>) F/C ratio per condition.</p>
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<p>Summary of water contact angles (WCA) and calculated total surface energy of uncoated and CF<sub>x</sub> a-C:H samples by studied duty cycle.</p>
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<p>AFM images of (5 µm × 5 µm, in height mode) of the CF<sub>x</sub>-coated a-C:H samples depending on the duty cycle used and their respective roughness values.</p>
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<p>ToF-SIMS imaging mode of CF<sub>x</sub>/a-C:H, CF<sub>x</sub>/a-C:H:Ag, and CF<sub>x</sub>/a-C:H:AgO sing 5.3% DC with F<sup>−</sup> and C<sub>4</sub>H<sup>−</sup> chosen as specific fragments representing the CF<sub>x</sub> layer and the a-C:H matrix, respectively.</p>
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<p>ToF-SIMS depth profile of 5.3CF<sub>x</sub>/a-C:H, 5.3CF<sub>x</sub>/a-C:H:Ag, and 5.3CF<sub>x</sub>/a-C:H:AgO showing F<sup>−</sup>, C<sub>4</sub>H<sup>−</sup>, 107Ag<sup>−</sup>, 109Ag<sup>−</sup>, and SiO<sub>2</sub><sup>−</sup> fragments representative of the CF<sub>x</sub> layer, the a-C:H matrix, Ag and AgO NPs, and the Si substrate.</p>
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<p>Release of silver ions (in mg/L) (<b>a</b>) before and (<b>b</b>) after CF<sub>x</sub> deposition. The figures show the results of a-C:H:Ag (12.1 ± 0.2 at. % Ag), a-C:H:AgO (11 ± 3 at. % Ag), 5.3CF<sub>x</sub>/a-C:H:Ag, and 5.3CF<sub>x</sub>/a-C:H:AgO coatings in deionized water for 30 days. MP-AES measurements limits (not shown): limit of detection (LOD) at 1 µg/L and limit of quantification (LOQ) at 5 µg/L.</p>
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<p>Percentage of <span class="html-italic">E. coli</span> growth after 12 h in contact with Si (as negative control) and modified coatings. The values were normalized to the Si substrate (* <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>SEM surface images of (<b>i</b>) Si, (<b>ii</b>) a-C:H:Ag, (<b>iii</b>) a-C:H:AgO, (<b>iv</b>) 5.3CF<sub>x</sub>/a-C:H:Ag, and (<b>v</b>) 5.3CF<sub>x</sub>/a-C:H:AgO collected after antibacterial assays with an acceleration voltage of 15 kV and at an amplification of 10,000×. The red arrows and circle are used to emphasize the presence of a disrupted cell wall on the surface of bacteria.</p>
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9 pages, 3053 KiB  
Communication
Exceptional Lithography Sensitivity Boosted by Hexafluoroisopropanols in Photoresists
by Junjun Liu, Dong Wang, Yitan Li, Haihua Wang, Huan Chen, Qianqian Wang and Wenbing Kang
Polymers 2024, 16(6), 825; https://doi.org/10.3390/polym16060825 - 15 Mar 2024
Viewed by 1059
Abstract
Advanced lithography requires highly sensitive photoresists to improve the lithographic efficiency, and it is critical, yet challenging, to develop high-sensitivity photoresists and imaging strategies. Here, we report a novel strategy for ultra-high sensitivity using hexafluoroisopropanol (HFIP)-containing fluoropolymer photoresists. The incorporation of HFIP, with [...] Read more.
Advanced lithography requires highly sensitive photoresists to improve the lithographic efficiency, and it is critical, yet challenging, to develop high-sensitivity photoresists and imaging strategies. Here, we report a novel strategy for ultra-high sensitivity using hexafluoroisopropanol (HFIP)-containing fluoropolymer photoresists. The incorporation of HFIP, with its strong electrophilic property and the electron-withdrawing effect of the fluorine atoms, significantly increases the acidity of the photoresist after exposure, enabling imaging without conventional photoacid generators (PAGs). The HFIP-containing photoresist has been evaluated by electron beam lithography to achieve a trench of ~40 nm at an extremely low dose of 3 μC/cm2, which shows a sensitivity enhancement of ~10 times compared to the commercial system involving PAGs, revealing its high sensitivity and high-resolution features. Our results demonstrate a new type of PAGs and a novel approach to higher-performance imaging beyond conventional photoresist performance tuning. Full article
(This article belongs to the Section Polymer Applications)
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<p>Comparison of UV and EBL performance of fluoropolymer-based photoresists with and without addition of conventional PAGs. (<b>a</b>,<b>d</b>,<b>g</b>,<b>j</b>) Photoresists S01~04 composed of polymers HF00, HF01, HF02, and HF03 and PAGs, respectively. (<b>b</b>,<b>c</b>) S05, (<b>e</b>,<b>f</b>) S06, (<b>h</b>,<b>i</b>) S07, and (<b>k</b>,<b>l</b>) S08 are photoresists composed of polymers HF00, HF01, HF02, HF03, respectively. Pitch and L/S of the designed layout are 400 nm and 3/1 (for EBL) and 60 μm and 4/1 (for UV), respectively.</p>
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<p>SEM images of photoresist patterns with a small feature size of sub-50 nm. (<b>a</b>) S03 and (<b>c</b>) S04 are photoresists using HF02 and PAGs and HF03 and PAGs, respectively. (<b>b</b>) S07 and (<b>d</b>) S08 are photoresists using HF02 and HF03, respectively.</p>
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<p>UV and XPS investigations. UV absorbance spectra of films composed of HF03 and a pH indicator bromocresol green before and after exposure to (<b>a</b>) UV light and (<b>b</b>) electron beam (30 kV). (<b>c</b>) C 1s spectra of HF03 film before and after exposure to electron beam (30 kV, 100 µC/cm<sup>2</sup>). (<b>d</b>) Calculated integral area of C-F from (<b>c</b>).</p>
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<p>Strategy for fluoropolymer photoresist patterning. (<b>a</b>) Approach to synthesizing fluoropolymers (HF01~03): the copolymerization of tert-butyl methacrylate (TBMA), p-acetoxystyrene (PACS), p-tert-butoxystyrene (PTBS), fluorinated monomers 2-((2,3,3,3-tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-(perfluoroethoxy)propoxy)propanoyl)oxy)ethyl methacrylate (M01), alpha, alpha-bis(trifluoromethyl)-4-vinylbenzyl alcohol (M02), and 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl methacrylate (M03). (<b>b</b>) Comparison of lithographic imaging performance of photoresists using different fluoropolymers.</p>
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<p>Proposed imaging mechanism of HFIP-containing fluoropolymer photoresists. (<b>a</b>) Dissociation of hydrogen ions. (<b>b</b>) Electrolytic dissociation and C-F bond cleavage, showing the formation of HF. (<b>c</b>) Acid-induced deprotection reaction.</p>
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10 pages, 2010 KiB  
Article
Nitroxide-Mediated Controlled Radical Copolymerization of α-Trifluoromethylstyrenes with Styrenes
by Tadashi Kanbara, Yuriko Ito, Airi Yamaguchi and Tomoko Yajima
Molecules 2024, 29(6), 1214; https://doi.org/10.3390/molecules29061214 - 8 Mar 2024
Viewed by 1088
Abstract
Fluorinated polymers are important materials in everyday life; however, most monomers of widely used fluoropolymers are gaseous, and their polymerization is difficult in an ordinary laboratory. Therefore, partially fluorinated polymers have recently been reported. As an easy-to-handle fluorine-containing monomer, α-trifluoromethylstyrene (TFMST) can be [...] Read more.
Fluorinated polymers are important materials in everyday life; however, most monomers of widely used fluoropolymers are gaseous, and their polymerization is difficult in an ordinary laboratory. Therefore, partially fluorinated polymers have recently been reported. As an easy-to-handle fluorine-containing monomer, α-trifluoromethylstyrene (TFMST) can be used to produce partially fluorinated polymers with trifluoromethyl groups in the main chain; however, TFMST does not homopolymerize, and there are limited reports on its copolymerization with styrene (ST). In this study, we applied the controlled radical polymerization method, which is effective for the polymerization of ST, to the copolymerization of TFMST and ST. We also showed that nitroxide-mediated polymerization is effective. The content ratio of TFMST in the TFMST–ST copolymer can be controlled between 10% and 40% by changing its monomer ratio. Additionally, the polymerization of TFMST and ST with substituents was performed to increase structural variations. The thermal stability as well as water and oil repellency of the synthesized polymers with different composition ratios and substituents were also evaluated. Full article
(This article belongs to the Special Issue Themed Issue Dedicated to Prof. Bernard Boutevin)
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<p>Plots of M<sub>n</sub> (down; blue dot), residual amount of TFMST (up; red dot (mol%)), and M<sub>w</sub>/M<sub>n</sub> (up; green dot) against reaction times; (<b>a</b>) ST to TFMST ratio of 90:10; (<b>b</b>) ST to TFMST ratio of 68:32.</p>
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<p>Water and oil contact angles of copolymers <b>5aa</b>, <b>5da</b>, and <b>5ad</b>.</p>
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21 pages, 5905 KiB  
Article
Investigating the Behavior of Thin-Film Formation over Time as a Function of Precursor Concentration and Gas Residence Time in Nitrogen Dielectric Barrier Discharge
by Faegheh Fotouhiardakani, Alex Destrieux, Jacopo Profili, Morgane Laurent, Sethumadhavan Ravichandran, Gowri Dorairaju and Gaetan Laroche
Materials 2024, 17(4), 875; https://doi.org/10.3390/ma17040875 - 14 Feb 2024
Cited by 1 | Viewed by 837
Abstract
This study aims to establish a correlation between the fragmentation process and the growth mechanisms of a coating deposited on a fluoropolymer. Deposition was carried out using dielectric barrier discharge at atmospheric pressure, employing an oxygen-containing organic precursor in a nitrogen environment. The [...] Read more.
This study aims to establish a correlation between the fragmentation process and the growth mechanisms of a coating deposited on a fluoropolymer. Deposition was carried out using dielectric barrier discharge at atmospheric pressure, employing an oxygen-containing organic precursor in a nitrogen environment. The findings reveal that the impact of precursor concentration on the formation of specific functionalities is more significant than the influence of treatment time. The X-ray photoelectron spectroscopy (XPS) results obtained indicate a reduction in the N/O ratio on the coating’s surface as the precursor concentration in the discharge increases. Fourier transform infrared spectroscopy (FTIR) analysis, conducted in the spectral range of 1500 cm−1 to 1800 cm−1, confirmed the connection between the chemical properties of plasma-deposited thin films and the concentration of organic precursors in the discharge. Furthermore, the emergence of nitrile moieties (C≡N) in the FTIR spectrum at 2160 cm−1 was noted under specific experimental conditions. Full article
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<p>(<b>a</b>) Current over one period for the different precursor concentrations; (<b>b</b>) corresponding Lissajous figures.</p>
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<p>(<b>a</b>) Typical C1s XPS spectra of the untreated ETFE and the surfaces after a long plasma treatment; (<b>b</b>) evolution of the survey and C1s XPS spectra as a function of the precursor concentration after 1 min of plasma treatment.</p>
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<p>Evolution of the XPS N/O and C–N, C–O/C–C, and C–H ratios as a function of the precursor concentration for a 1 min plasma treatment.</p>
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<p>Fourier-transform infrared spectra of untreated ETFE and plasma-treated ETFE samples after 3 min using 1 SLM total flow containing 1% precursor.</p>
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<p>Curve fitting (red lines) of FTIR spectrum (Black lines) in the region between 1500 cm<sup>−1</sup> and 1800 cm<sup>−1</sup>.</p>
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<p>Evolution of the C=O amide and ketone as a function of precursor concentration (<b>a</b>) after 1 min of plasma treatment and (<b>b</b>) after 7 min of plasma treatment.</p>
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<p>Evolution of the amide/ketone ratio as a function of precursor concentration over time (e.g., 1, 3, 5, and 7 min): (<b>a</b>) 1 SLM total flow (Ƭr: 8.5 ms); (<b>b</b>) 5 SLM total flow (Ƭr: 1.7 ms).</p>
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<p>FTIR spectra of plasma-treated ETFE showing the evolution of the absorbance of the C≡N feature’s (2160 cm<sup>−1</sup>) evolution over time for (<b>a</b>) 1% precursor under a 1 SLM total flow; (<b>b</b>) 3% precursor under a 1 SLM total flow; (<b>c</b>) 3% precursor under a 5 SLM total flow; (<b>d</b>) 5% precursor under a 5 SLM total flow.</p>
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<p>Normalized infrared absorbance of the C≡N intensity with respect to coating thickness as a function of treatment time for the following experimental conditions: black—1 SLM 1% precursor concentration (Ƭr = 8.5 ms); red—5 SLM-3% precursor concentration (Ƭr = 1.7 ms).</p>
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<p>(<b>a</b>) Coating thickness (nm); (<b>b</b>) growth rate evolution (nm/min) for 18 g·h<sup>−1</sup> precursor amount as a function of treatment time for the following residence times: blue—Ƭr = 8.5 ms (1 SLM total flow); red—Ƭr = 1.7 ms (5 SLM total flow).</p>
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<p>(<b>a</b>) Coating thickness (nm); (<b>b</b>) growth rate evolution (nm/min) as a function of treatment time for 3%, 10%, and 15% precursor under a 5 SLM total flow.</p>
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18 pages, 4028 KiB  
Article
Wear-Resistant Elastomeric Composites Based on Unvulcanized Rubber Compound and Recycled Polytetrafluoroethylene
by Oksana Ayurova, Vasiliy Kornopoltsev, Andrey Khagleev, Roman Kurbatov, Undrakh Mishigdorzhiyn, Afanasiy Dyakonov and Dmitriy Mognonov
Lubricants 2024, 12(2), 29; https://doi.org/10.3390/lubricants12020029 - 24 Jan 2024
Viewed by 1621
Abstract
Advancements in industrial machinery and manufacturing equipment require more reliable and efficient polymer tribo-systems which operate in conditions associated with increasing machine speeds and a lack of cooling oil. The goal of the current research is to improve the tribological properties of elastomeric [...] Read more.
Advancements in industrial machinery and manufacturing equipment require more reliable and efficient polymer tribo-systems which operate in conditions associated with increasing machine speeds and a lack of cooling oil. The goal of the current research is to improve the tribological properties of elastomeric composites by adding a solid lubricant filler in the form of ultrafine polytetrafluoroethylene (PTFE) with the chemical formula [C2F4]n and recycled polytetrafluoroethylene (r-PTFE) powders. PTFE waste is recycled mechanically by abrasion. The elastomeric composites are prepared by mixing a nitrile butadiene rubber with a phenol-formaldehyde resin and PTFE powders in an extruder followed by rolling. The deformation-strength and tribological tests of r-PTFE elastomeric composites are conducted in comparison with the ultrafine PTFE composites. The latter is based on products of waste fluoropolymer processing using a radiation method. The deformation-strength test shows that the introduction of ultrafine PTFE and r-PTFE powder to the composite leads to a decrease in strength and elongation at break, which is associated with the poor compatibility of additives and the elastomeric matrix. The friction test indicates a decrease in the coefficient of friction of the composite material. It is determined that the 15 wt.% filler added in the elastomeric matrix leads to a reduction in the wear rate by 20%. The results obtained show the possibility of using ultrafine PTFE powder and r-PTFE for creating elastomeric composites with increased tribological properties. These research results are beneficial for rubber products used in many industries, mainly in mechanical engineering. Full article
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<p>The procedure of elastomeric composite fabrication.</p>
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<p>Microphotographs of PTFE powders: (<b>a</b>,<b>b</b>) r-PTFE; (<b>c</b>,<b>d</b>) TOMFLON<sup>TM</sup>.</p>
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<p>Microphotographs of PTFE powders: (<b>a</b>,<b>b</b>) r-PTFE; (<b>c</b>,<b>d</b>) TOMFLON<sup>TM</sup>.</p>
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<p>XRD patterns of the studied fluoropolymers.</p>
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<p>XRD patterns: (<b>a</b>) modeling of the peaks of the crystalline phase for the WPTFE sample; (<b>b</b>) modeling of halo of amorphous phases; (<b>c</b>) modeling of the entire radiograph, where blue line is experimental X-ray diffraction pattern indicated, red line is calculated radiograph indicated, gray line is difference radiograph, and lilac line is profiles of all reflections, assigned to both the crystalline component of the sample and the amorphous one.</p>
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<p>XRD patterns: (<b>a</b>) modeling of the peaks of the crystalline phase for the WPTFE sample; (<b>b</b>) modeling of halo of amorphous phases; (<b>c</b>) modeling of the entire radiograph, where blue line is experimental X-ray diffraction pattern indicated, red line is calculated radiograph indicated, gray line is difference radiograph, and lilac line is profiles of all reflections, assigned to both the crystalline component of the sample and the amorphous one.</p>
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<p>TG (<b>a</b>) and DSC (<b>b</b>) curves: 1—WPTFE; 2—r-PTFE; 3—TOMFLON<sup>TM</sup>.</p>
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<p>SEM micrographs and elemental composition of elastomeric composites with 10 wt.% PTFE content: (<b>a</b>) URC/PhFR/TOMFLON<sup>TM</sup>; (<b>b</b>) URC/PhFR/r-PTFE.</p>
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<p>SEM micrographs and elemental composition of elastomeric composites with 20 wt.% PTFE content: (<b>a</b>) URC/PhFR/TOMFLON<sup>TM</sup>; (<b>b</b>) URC/PhFR/r-PTFE.</p>
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<p>TG curves of polymer–polymer mixture and elastomeric composites: 1—URC/PhFR; 2—URC/PhFR/TOMFLON<sup>TM</sup>; 3—URC/PhFR/r-PTFE.</p>
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<p>Deformation-strength properties of elastomeric composites 1—URC/PhFR/TOMFLON<sup>TM</sup> and 2—URC/PhFR/r-PTFE depending on the content of antifriction filler: (<b>a</b>) tensile strength, MPa; (<b>b</b>) relative elongation at break, %.</p>
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<p>Coefficient of friction of an elastomeric composite depending on the content of antifriction filler: 1—URC/PhPR/r-PTFE; 2—URC/PhPR/TOMFLON<sup>TM</sup>.</p>
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<p>Wear rate of the elastomeric composite depending on the content of antifriction filler: 1—URC/PhPR/r-PTFE; 2—URC/PhPR/TOMFLON<sup>TM</sup>.</p>
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15 pages, 7075 KiB  
Article
Hydrophilic Nature of Polytetrafluoroethylene through Modification with Perfluorosulfonic Acid-Based Polymers
by Shakila Parveen Asrafali, Thirukumaran Periyasamy and Seong-Cheol Kim
Sustainability 2023, 15(23), 16479; https://doi.org/10.3390/su152316479 - 1 Dec 2023
Cited by 1 | Viewed by 1141
Abstract
Polytetrafluoroethylene (PTFE), commercially known as Teflon, is a fluoropolymer with a structure containing (CF2–CF2)n. It has high resistance to acids, alkalis and corrosive chemicals. PTFE is hydrophobic in nature with a water contact angle of 140°. Being [...] Read more.
Polytetrafluoroethylene (PTFE), commercially known as Teflon, is a fluoropolymer with a structure containing (CF2–CF2)n. It has high resistance to acids, alkalis and corrosive chemicals. PTFE is hydrophobic in nature with a water contact angle of 140°. Being hydrophobic in nature is a knotty problem, particularly in electrical applications, as it may lead to short circuits and result in reducing the lifetime of electrical equipment. Herein we describe the surface modification of PTFE from hydrophobic to hydrophilic without altering its bulk property. The surface hydrophilicity is achieved by two different techniques, viz., polymer coating (aquivion and nafion) and plasma treatment. Several characterization techniques including FTIR, Raman, XPS, WCA and SEM were used to analyze the surface of PTFE. It was found that 5% of the polymer solution and N2 plasma treatment for 2 min can produce huge differences in the surface property, as evidenced by the reduction in water contact angle from 140° (neat Teflon) to 80° (surface-modified Teflon). The surface morphology of neat PTFE is completely changed and collapsed as evidenced by the SEM images. The FTIR, Raman and XPS analyses confirm the presence of additional hydrophilic functional groups after the polymer coating and plasma treatment. Hence, this method represents a unique approach to modifying the surface property of Teflon, while maintaining its bulk property. Full article
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<p>FT-IR spectra of untreated PTFE and plasma-treated PTFE with aquivion.</p>
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<p>FT-IR spectra of untreated PTFE and plasma-treated PTFE with nafion.</p>
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<p>Raman spectra of untreated PTFE and plasma-treated PTFE with aquivion and nafion.</p>
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<p>Water contact angle values (<b>A</b>), images (<b>B</b>) [PTFE: (<b>a</b>,<b>a′</b>), aquivion-coated PTFE: (<b>b</b>–<b>e</b>), nafion-coated PTFE: (<b>f</b>–<b>i</b>)] and (<b>C</b>) the atomic concentration of the untreated PTFE and modified PTFE.</p>
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<p>XPS analysis showing the survey spectra of (a) untreated PTFE; (b) plasma treated PTFE with aquivion; and (c) plasma treated PTFE with nafion.</p>
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<p>XPS analysis showing the deconvoluted spectra of untreated PTFE (<b>a</b>–<b>c</b>); PTFE modified with aquivion (<b>d</b>–<b>f</b>); and PTFE modified with nafion (<b>g</b>–<b>i</b>).</p>
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<p>SEM images of (<b>a</b>) untreated PTFE; (<b>b</b>–<b>e</b>) PTFE modified with aquivion; and (<b>f</b>) the EDX spectrum of PTFE modified with aquivion.</p>
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<p>SEM images of (<b>a</b>) untreated PTFE; (<b>b</b>–<b>e</b>) PTFE modified with nafion; and (<b>f</b>) the EDX spectrum of PTFE modified with nafion.</p>
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<p>Water contact angle images of plasma-treated PTFE with (<b>a</b>) aquivion and (<b>b</b>) nafion preserved for 1 week.</p>
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<p>Chemical resistivity of untreated PTFE in (<b>a</b>) 2N HCl and (<b>b</b>) 2N NaOH; PTFE_Aq_120s in (<b>c</b>) 2N HCl and (<b>d</b>) 2N NaOH; and PTFE_Naf_120s in (<b>e</b>) 2N HCl and (<b>f</b>) 2N NaOH. The respective dried samples (<b>g</b>–<b>l</b>).</p>
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<p>Schematic representation showing the surface modification process of PTFE.</p>
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33 pages, 7062 KiB  
Review
Fluoropolymers as Unique and Irreplaceable Materials: Challenges and Future Trends in These Specific Per or Poly-Fluoroalkyl Substances
by Bruno Améduri
Molecules 2023, 28(22), 7564; https://doi.org/10.3390/molecules28227564 - 13 Nov 2023
Cited by 12 | Viewed by 3810
Abstract
In contrast to some low-molar-mass per- and polyfluoroalkyl substances (PFASs), which are well established to be toxic, persistent, bioaccumulative, and mobile, fluoropolymers (FPs) are water-insoluble, safe, bioinert, and durable. These niche high-performance polymers fulfil the 13 polymer-of-low-concern (PLC) criteria in their recommended conditions [...] Read more.
In contrast to some low-molar-mass per- and polyfluoroalkyl substances (PFASs), which are well established to be toxic, persistent, bioaccumulative, and mobile, fluoropolymers (FPs) are water-insoluble, safe, bioinert, and durable. These niche high-performance polymers fulfil the 13 polymer-of-low-concern (PLC) criteria in their recommended conditions of use. In addition, more recent innovations (e.g., the use of non-fluorinated surfactants in aqueous radical (co)polymerization of fluoroalkenes) from industrial manufacturers of FPs are highlighted. This review also aims to show how these specialty polymers endowed with outstanding properties are essential (even irreplaceable, since hydrocarbon polymer alternatives used in similar conditions fail) for our daily life (electronics, energy, optics, internet of things, transportation, etc.) and constitute a special family separate from other “conventional” C1–C10 PFASs found everywhere on Earth and its oceans. Furthermore, some information reports on their recycling (e.g., the unzipping depolymerization of polytetrafluoroethylene, PTFE, into TFE), end-of-life FPs, and their risk assessment, circular economy, and regulations. Various studies are devoted to environments involving FPs, though they present a niche volume (with a yearly production of 330,300 t) compared to all plastics (with 460 million t). Complementary to other reviews on PFASs, which lack of such above data, this review presents both fundamental and applied strategies as evidenced by major FP producers. Full article
(This article belongs to the Section Materials Chemistry)
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<p>Historical scheme of the fluorochemicals, from the discovery of polytetrafluoroethylene (PTFE) to REACH regulations (Reprinted with permission from Ref. [<a href="#B9-molecules-28-07564" class="html-bibr">9</a>]. Copyright 2022 Royal Society of Chemistry) (APFO, ECF, EPA, FT, PFBS, PFCA, PFNA, PFOA, PFOS, POP, and REACH stand for ammonium perfluorooctanoate, electrochemical fluorination, Environment Protection Agency, fluorotelomer, perfluorobutanesulfonate, perfluorocarboxylic acid, perfluorononanoic acid, perfluorooctanoic acid, perfluorooctanesulfonic acid, persistant organic pollutants, and Registration, Evaluation, Authorisation and Restriction of Chemicals, respectively.</p>
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<p>Mass budget for PFASs in groundwater below the fire training area at Joint Base Cape Cod, USA: Comparison of detected extractable organofluorine (EOF) and PFAS concentrations. The <span class="html-italic">x</span>-axis represents the sum of terminal PFAS and oxidizable precursors inferred from the total oxidizable precursor (TOP) assay using Bayesian inference. The sum of differences from duplicate extracts for targeted PFAS (9%; <span class="html-italic">n</span> = 1) and the standard deviation of inferred precursor concentrations are shown by <span class="html-italic">x</span>-axis error bars. Circles are shaded in purple according to the fraction of EOF explained by oxidizable precursors. The one-tone line (gray) is used to compare the sum of terminal PFASs and precursors measured using targeted analysis and the TOP inference with EOF. Reprinted with permission from Ref. [<a href="#B24-molecules-28-07564" class="html-bibr">24</a>].</p>
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<p>General classification of PFASs according to the Organization for Economic Co-operation and Development (OECD) [<a href="#B1-molecules-28-07564" class="html-bibr">1</a>].</p>
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<p>Synthesis of fluoropolymer nanoparticle (FPNP)-embedded hydrogel and study on PFAS adsorption. Adapted with permission from Ref. [<a href="#B54-molecules-28-07564" class="html-bibr">54</a>]. Copyright 2020 American Chemical Society.</p>
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<p>Compared relative heat and oil resistances of elastomers (ASTM D2000). Adapted with permission from Ref. [<a href="#B69-molecules-28-07564" class="html-bibr">69</a>]. Copyright 2003 Elsevier.</p>
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<p>Regulatory decision tree for fluoropolymers. Reprinted from Ref. [<a href="#B101-molecules-28-07564" class="html-bibr">101</a>].</p>
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<p>Sketch of the world’s first pilot plant for recycling perfluorinated polymers in Germany. Reprinted with permission from Ref. [<a href="#B145-molecules-28-07564" class="html-bibr">145</a>]. Copyright 2016 3M/Dyneon GmbH.</p>
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<p>Perfluorosulfonic acid (PFSA) for PEMFC membranes used in fuel cells and electrolyzers. Reprinted with permission from Ref. [<a href="#B154-molecules-28-07564" class="html-bibr">154</a>]. Copyright 2016 Royal Society of Chemistry.</p>
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<p>Reaction scheme of the thermal depolymerization of poly(2,2,2-trifluoroethylacrylate), PTFEMA, and <sup>1</sup>H NMR spectra of PTFEMA (up), of the total product mixture after 8 h (middle spectrum), and of TFEMA after depolymerization (bottom). Adapted from Ref. [<a href="#B161-molecules-28-07564" class="html-bibr">161</a>].</p>
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<p>Engineering drawing of the “<span class="html-italic">Brennkammer mit Dampfkessel</span>” (BRENDA) (German acronym) pilot combustion facility at Karlsruhe Institute of Technology. Reprinted with permission from Ref. [<a href="#B174-molecules-28-07564" class="html-bibr">174</a>]. Copyright 2019 Elsevier.</p>
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<p>Fate of collected FP waste and tonnages (percentages) involved in recycling, recovery, reuse, and landfill in EU. Reprinted with permission from Ref. [<a href="#B134-molecules-28-07564" class="html-bibr">134</a>]. Copyright 2020 Conversio Market &amp; Strategy GmbH.</p>
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<p>Sketch of flows of materials in a circular economy. Reprinted with permission from Ref. [<a href="#B165-molecules-28-07564" class="html-bibr">165</a>]. Copyright 2021 European Topic Centre Waste and Materials in a Green Economy.</p>
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<p>Circular economy situation of FPs: lifecycle of FPs from feedstocks extraction to end of life in EU. Reprinted with permission from Ref. [<a href="#B134-molecules-28-07564" class="html-bibr">134</a>]. Copyright 2020 Conversio Market &amp; Strategy GmbH.</p>
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<p>Cycle of fluorine chemistry from fluorspar (CaF<sub>2</sub>) to PTFE, along with potential routes for recycling, including thermal depolymerization (above 500 °C), selective defluorination to form fluorinating agents, and complete destruction back to inorganic metal fluoride. Reprinted from Ref. [<a href="#B187-molecules-28-07564" class="html-bibr">187</a>].</p>
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<p>Illustration of microbial degradation of poly(fluoroacrylate) that generates 8:2 fluorotelomer derivatives. Adapted with permission from Ref. [<a href="#B43-molecules-28-07564" class="html-bibr">43</a>]. Copyright 2013 Elsevier.</p>
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<p>Thermal decomposition of PTFE in absence or presence of various metals or salts to lead back to TFE (and other fluorinated compounds) [<a href="#B142-molecules-28-07564" class="html-bibr">142</a>,<a href="#B143-molecules-28-07564" class="html-bibr">143</a>]. The recovered TFE was homopolymerized [<a href="#B157-molecules-28-07564" class="html-bibr">157</a>], or copolymerized with HFP [<a href="#B158-molecules-28-07564" class="html-bibr">158</a>] or isobutyl vinyl ether (iBuVE) [<a href="#B159-molecules-28-07564" class="html-bibr">159</a>], to produce PTFE, poly(TFE-<span class="html-italic">co</span>-HFP) copolymer (i.e., FEP), or alternated poly(TFE-<span class="html-italic">co</span>-iBuVE) copolymer [<a href="#B159-molecules-28-07564" class="html-bibr">159</a>].</p>
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<p>Proposed mechanism for the H<sub>2</sub>O<sub>2</sub>-induced decomposition of PVDF. Reprinted from Ref. [<a href="#B180-molecules-28-07564" class="html-bibr">180</a>].</p>
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<p>Proposed procedure for the mineralization of PTFE using molten NaOH.</p>
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<p>Room-temperature reaction of a nucleophilic magnesium reagent (<b>1</b>) with PTFE to generate an organometallic fluorinated magnesium complex (<b>2</b>). Reprinted from Ref. [<a href="#B187-molecules-28-07564" class="html-bibr">187</a>].</p>
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14 pages, 3448 KiB  
Article
Ion-Selective Membranes Fabricated Using Finely Controlled Swelling of Non-Ionic Fluoropolymer for Redox Flow Batteries
by Fengjing Jiang and Rui Xue
Batteries 2023, 9(11), 545; https://doi.org/10.3390/batteries9110545 - 6 Nov 2023
Viewed by 1812
Abstract
Ion-selective membranes based on non-ionic polymers are promising for redox flow batteries due to their superior chemical stability and low cost. In this work, a poly(vinylidene fluoride) (PVDF) ion-selective membrane is successfully prepared using a solvent-controlled swelling method, where Nafion is used as [...] Read more.
Ion-selective membranes based on non-ionic polymers are promising for redox flow batteries due to their superior chemical stability and low cost. In this work, a poly(vinylidene fluoride) (PVDF) ion-selective membrane is successfully prepared using a solvent-controlled swelling method, where Nafion is used as a channel-forming promoter. The influences of Nafion on the channel formation of the membranes are studied. The results indicate that the addition of Nafion resin can greatly promote the formation of ion-conducting channels in the PVDF matrix. The obtained membranes show well-controlled proton conductivity and proton/vanadium selectivity. A battery test on a vanadium redox flow single cell is successfully performed. The energy efficiency of the cell equipped with the PVDF-based ion-selective membrane reaches 81.7% at a current density of 60 mA cm−2 and possesses excellent cycling stability and suppressed self-discharge after modification with Nafion. Full article
(This article belongs to the Special Issue Energy Storage of Redox-Flow Batteries)
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<p>Schematic diagram of the gel-solidification method.</p>
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<p>Photo of the prepared PVDF-based ion-selective membrane.</p>
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<p>Influence of Nafion content on (<b>a</b>) apparent porosity, (<b>b</b>) conductivity, and (<b>c</b>) vanadium ion permeability of PVDF-based ion-selective membranes.</p>
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<p>Polarizing micrographs of (<b>a</b>) PVDF, (<b>b</b>) PVDF-Nafion-5, (<b>c</b>) PVDF-Nafion-10, and (<b>d</b>) PVDF-Nafion-20.</p>
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<p>Dependance of (<b>a</b>) apparent porosity, (<b>b</b>) conductivity, and (<b>c</b>) vanadium ion permeability of the PVDF-based membranes on the solvent ratio of the swelling agent.</p>
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<p>(<b>a</b>) Stress–strain curves and (<b>b</b>) stress at break of the PVDF-Nafion-10 membrane with various apparent porosities.</p>
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<p>CE, VE, and EE of the VRFB single cell at various current densities.</p>
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<p>(<b>a</b>) Efficiency and (<b>b</b>) capacity of the VRFB single cell equipped with the porous PVDF membrane during the cycling test measured at 100 mA cm<sup>−2</sup>.</p>
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<p>Self-discharge curves of PVDF-Nafion-10 and PVDF.</p>
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16 pages, 11845 KiB  
Article
Fast Forward: Optimized Sample Preparation and Fluorescent Staining for Microplastic Detection
by Michael Toni Sturm, Erika Myers, Anika Korzin, Sabrina Polierer, Dennis Schober and Katrin Schuhen
Microplastics 2023, 2(4), 334-349; https://doi.org/10.3390/microplastics2040026 - 22 Oct 2023
Cited by 3 | Viewed by 2170
Abstract
The fast, affordable, and standardized detection of microplastics (MP) remains one of the biggest challenges in MP research. Comparable data are essential for appropriate risk assessments and the implementation of laws and limit values. The fluorescent staining of MP in environmental samples is [...] Read more.
The fast, affordable, and standardized detection of microplastics (MP) remains one of the biggest challenges in MP research. Comparable data are essential for appropriate risk assessments and the implementation of laws and limit values. The fluorescent staining of MP in environmental samples is a possible solution to this problem. This study investigates the optimization of a sample preparation process (hydrogen peroxide digestion) and the staining process (temperature, concentration, time, surfactants as staining aids) for using a specifically developed fluorescent dye for MP detection. The optimization is performed by comparing the sample preparation process and staining of MP from different polymers and natural particles. Further, the suitability of the optimized process for the detection of fluoropolymers and tire abrasion was tested. The results show that the optimized method (increased temperature and optimized stain concentration) can detect microplastics reliably with a total sample preparation and measurement time of 2.5–3 h per sample, reaching recovery rates of 93.3% (polypropylene) to 101.7% (polyester). Moreover, two of the three tested fluoropolymers could be detected reliably. Tire abrasion could not be detected with the here presented method, as the black color leads to strong quenching. A long-term study measuring the MP pollution in the effluent of a municipal wastewater treatment plant compared the optimized and original processes and confirmed the stability of the improved method for routine measurements and contamination control. Full article
(This article belongs to the Collection Current Opinion in Microplastics)
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<p>Importance of microplastics detection for scientists, politics, the public, and industries.</p>
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<p>Influence of staining time—fluorescent images of microplastics from different polymers stained with 0.5 mg/L of abcr eco Wasser 3.0 detect mix MP-1 at 5 °C for different times (1 h; 5 h; 24 h).</p>
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<p>Influence of staining temperature—fluorescent images of microplastics from different polymers stained with 0.5 mg/L of abcr eco Wasser 3.0 detect mix MP-1 for 1 h at different temperatures (25 °C; 80 °C).</p>
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<p>Influence of stain concentration—fluorescent images of microplastics from different polymers stained with abcr eco Wasser 3.0 detect mix MP-1 for 1 h at 80 °C with different stain concentrations (0.05 mg/L; 0.25 mg/L; 0.5 mg/L).</p>
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<p>Fluorescent images of stained fluoropolymers—fluorescent images of microplastics from different fluoropolymers stained with 0.25 mg/L of abcr eco Wasser 3.0 detect mix MP-1 for 1 h at 80 °C. FEP = Fluorethylenpropylene; ETFE = Ethylen-Tetrafluorethylene; PVDF = Polyvinylidene fluoride.</p>
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<p>Fluorescent images of stained tire and rubber particles—fluorescent images of microplastics from tire and rubber particles stained with 0.25 mg/L of abcr eco Wasser 3.0 detect mix MP-1 for 1 h at 80 °C. SBR = Styrene-butadiene rubber, NR = Natural rubber, SBR-NR = blend of SBR and NR.</p>
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<p>Optimized hydrogen peroxide treatment—recovery rates of microplastics and natural particles after a hydrogen peroxide digestion and fluorescent staining with 0.25 mg/L of abcr eco Wasser 3.0 detect mix MP-1 for 1 h at 80 °C. (<b>a</b>) Hydrogen peroxide treatment for 4 h at 80 °C and 20 h at RT; (<b>b</b>) hydrogen peroxide treatment for 1 h at 100 °C.</p>
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<p>Comparison of wastewater effluent samples processed with the original method (slow method) compared to the accelerated method (fast method) with faster hydrogen peroxide treatment and staining.</p>
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<p>Photos and fluorescent images of the processed and stained wastewater samples using the fast method. (<b>a</b>) Photo of the sample from 13 June 2023. (<b>b</b>) Fluorescent image of the sample from 13 June 2023. (<b>c</b>) Photo of the sample from 15 June 2023 (<b>d</b>) Fluorescent image of the sample from 15 June 2023.</p>
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