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20 pages, 18781 KiB  
Article
Demonstration of Pattern Size Effects on Hydrophobic Nanocellulose Coatings with Regular Micron-Sized Island-like Geometrical Domains Created by Femtosecond Laser Micromachining
by Pieter Samyn, Patrick Cosemans and Olivier Malek
Micromachines 2025, 16(3), 289; https://doi.org/10.3390/mi16030289 - 28 Feb 2025
Viewed by 123
Abstract
As inspired by nature, wettability of bio-based material surfaces can be controlled by combining appropriate surface chemistries and topographies mimicking the structure of plant leaves or animals. The need for bio-based nanocellulose coatings with enhanced hydrophobic properties becomes technically relevant for extending their [...] Read more.
As inspired by nature, wettability of bio-based material surfaces can be controlled by combining appropriate surface chemistries and topographies mimicking the structure of plant leaves or animals. The need for bio-based nanocellulose coatings with enhanced hydrophobic properties becomes technically relevant for extending their applications in the technological domain with better protection and lifetime of the coatings. In this work, the water repellence of spray-coated nanocellulose coatings with hydrophobically modified cellulose microfiber (mCMF coatings), or hydrophobically modified cellulose nanofiber (mCNF coatings) was enhanced after femtosecond laser patterning. In particular, the influences of different island-like pattern geometries and pattern sizes were systematically studied. The island-like patterns were experimentally created with single posts that have variable sizes of the valleys (B = 30 to 15 µm) and top surface area (T = 120 to 15 µm), resulting in good resolution of the patterns down to the size of the laser beam diameter (15 µm). Depending on the intrinsic homogeneity and porosity of sprayed mCMF and mCNF coatings, the quality and resolution of the island-like patterns is better for the mCNF coatings with thinner and more homogeneous sizes of the cellulose nanofibrils. The increase in apparent water contact angle on patterned nanocellulose coatings can be estimated from the theoretical Cassie–Baxter state of wetting and shows maximum values up to θs = 128° (mCMF coatings), or θs = 140° (mCNF coatings), for the smallest pattern sizes in parallel with minimum contact angle hysteresis of Δθ = 14° (mCMF coatings), or Δθ < 9° (mCNF coatings). The study demonstrated that femtosecond laser patterning technology provides high flexibility and adaptivity to create surface patterns in appropriate dimensions with enhanced hydrophobicity of nanocellulose coatings. Full article
(This article belongs to the Special Issue Laser Micro/Nano-Fabrication)
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Figure 1

Figure 1
<p>Schematic representation of the laser beam path focusing on the sample set-up used for the femtosecond laser patterning.</p>
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<p>Spatial overlap between single laser pulses as determined by the net effective pulse number <span class="html-italic">η:</span> (<b>a</b>) No pulse overlap, <span class="html-italic">η</span> &lt; 1; (<b>b</b>) Pulse touching, <span class="html-italic">η</span> = 1; (<b>c</b>) Pulse overlap <span class="html-italic">η</span> &gt; 1.</p>
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<p>Schematic picture for creation of island-like geometrical domains with different sizes: (<b>a</b>) Representation of a single square post with dimensions H, B, T; (<b>b</b>) Path of the laser beam with spacing of the laser spot and overlap rate, with selection of hatch pitch hx, hy in respective X- and Y-direction; (<b>c</b>) Selection of smaller hatch pitch hx, hy in respective X- and Y-direction; (<b>d</b>) Selection of an offset value Δhx, Δhy for the hatch pitch during two subsequent laser ablation steps, (<b>e</b>) Selection of an offset value Δhx, Δhy for the hatch pitch during three subsequent laser ablation steps. The latter multiple laser processing steps are applied to increase B sizes and decrease T sizes.</p>
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<p>Confocal laser microscopy of sprayed nanocellulose coatings before laser patterning: (<b>a</b>) Hydrophobic cellulose microfiber coatings (mCMF); (<b>b</b>) Hydrophobic cellulose nanofiber coatings (mCNF), with laser image (<b>top</b>) and 3D topographical image (<b>bottom</b>) in two magnifications (50×, 150× objective lens). The z-scale range applies to all topographical images.</p>
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<p>Confocal laser interferometry of island-like domains on mCMF coatings created by femtosecond laser patterning with different geometrical dimensions of individual posts with selected T, B sizes (series according to <a href="#micromachines-16-00289-t001" class="html-table">Table 1</a>).</p>
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<p>Confocal laser interferometry of island-like domains on mCNF coatings created by femtosecond laser patterning with different geometrical dimensions of individual posts with selected T, B sizes (series according to <a href="#micromachines-16-00289-t001" class="html-table">Table 1</a>).</p>
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<p>Detailed microscopic observation of femtosecond laser-patterned mCMF coatings with an example of single island-like domains: (<b>a</b>) Local microscopy of island-like domains with sizes B = 15 µm, T = 50 µm (series 01), laser intensity image; (<b>b</b>) Long-range detail and island-like domains with sizes B = T = 20 µm (series 03), optical image; (<b>c</b>) Height profile over several posts on mCMF coatings.</p>
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<p>Detailed microscopic observation of femtosecond laser-patterned mCNF coatings with an example of single island-like domains: (<b>a</b>) Local microscopy of island-like domains with sizes B = 15 µm, T = 50 µm (series 01), laser intensity image; (<b>b</b>) Long-range detail and island-like domains with sizes B = T = 20 µm (series 03), optical image; (<b>c</b>) Height profile over several posts on mCNF coatings.</p>
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<p>Height dimensions (H) of individual posts on island-like geometrical patterns for mCMF coatings (black bar) and mCNF coatings (gray bar), as experimentally determined from profilometry measurements.</p>
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<p>Three-dimensional topographical images of island-like domains on mCNF coatings created by femtosecond laser patterning with different geometrical dimensions of individual posts according to the selected T, B sizes (series according to <a href="#micromachines-16-00289-t001" class="html-table">Table 1</a>). Same color applies for all Z scales.</p>
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<p>Theoretical model calculations following the Cassie–Baxter equation of apparent contact angles <span class="html-italic">θ*</span> to be expected on mCMF coatings (open symbols, o) and mCNF coatings (closed symbols, ●), after island-like patterning with different H, B, T sizes of individual posts (see insets). The calculated values for <span class="html-italic">θ*</span> are plotted as a function of (<b>a</b>) H/B ratio, (<b>b</b>) B/T ratio, and (<b>c</b>) H/T ratio.</p>
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<p>Hydrophobic properties of patterned mCMF coatings with island-like geometries of different B, T size (series according to <a href="#micromachines-16-00289-t001" class="html-table">Table 1</a>): (<b>a</b>) Static water contact angles <span class="html-italic">θ*</span> (theoretical calculations in black bar, experimental value in gray bar); (<b>b</b>) Contact angle hysteresis of water Δ<span class="html-italic">θ</span> (difference in advancing and receding contact angles).</p>
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<p>Hydrophobic properties of patterned mCNF coatings with island-like geometries of different B, T size (series according to <a href="#micromachines-16-00289-t001" class="html-table">Table 1</a>): (<b>a</b>) Static water contact angles <span class="html-italic">θ*</span> (theoretical calculations in black bar, experimental value in gray bar); (<b>b</b>) Contact angle hysteresis of water Δ<span class="html-italic">θ</span> (difference in advancing and receding contact angles).</p>
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<p>Comparative graph for values of apparent water contact angles, including theoretical values (Cassie–Baxter model) versus experimental values on patterned mCMF coatings (open symbols, o) and patterned mCNF coatings (closed symbols, ●).</p>
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15 pages, 11779 KiB  
Article
Electrospun Polycaprolactone (PCL) Nanofibers Induce Elongation and Alignment of Co-Cultured Primary Cortical Astrocytes and Neurons
by Kayleigh Nutt, Zoe Dombros-Ryan, Ruxandra Birea, Emily Victoria Franks, Sarah Eastham, Morgan Godwin, Chris F. Adams, Divya Maitreyi Chari and Stuart Iain Jenkins
Micromachines 2025, 16(3), 256; https://doi.org/10.3390/mi16030256 - 25 Feb 2025
Viewed by 454
Abstract
Neuromimetic in vitro models, simulating in vivo architecture/organization, are urgently needed to reduce experimental reliance on live animals. Our group recently reported a novel brain tissue derivation protocol, simultaneously deriving all major cortical cell types (including immune cells) in a facile protocol, generating [...] Read more.
Neuromimetic in vitro models, simulating in vivo architecture/organization, are urgently needed to reduce experimental reliance on live animals. Our group recently reported a novel brain tissue derivation protocol, simultaneously deriving all major cortical cell types (including immune cells) in a facile protocol, generating a network of neurons in a single growth medium, which was interfaced with nanomaterials. This represents a significant advance, as tissue engineers overwhelmingly use diverse methods to derive and combine individual brain cells for materials-interfacing. However, this multicellular model lacked cellular directionality/structural organization (unlike the highly organized cortical circuits in vivo). Synthetic nanofiber constructs are of high value in tissue engineering, providing directional cues for cells. Most neuro-nanofiber studies employ simple monocultures of astrocytes/neurons and commonly use peripheral neurons rather than central nervous system populations. Here, we have interfaced our complex brain model (neurons/astrocytes derived simultaneously) with randomly oriented or aligned polycaprolactone (PCL) fiber meshes. Both cell types showed targeted extension along aligned fibers versus coverslips or random fibers. A new analysis method developed in-house demonstrated that peak orientations for astrocytes and neurons correlated with aligned nanofibers. Our data support the concept that nanofiber scaffolds can achieve organized growth of mixed cortical neural cell populations, mimicking neural architecture. Full article
(This article belongs to the Special Issue The 15th Anniversary of Micromachines)
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Figure 1

Figure 1
<p>Diameter and orientation of polycaprolactone fiber constructs. Scanning electron micrographs of randomly oriented (<b>a</b>) and aligned (<b>b</b>) PCL nanofiber constructs. (<b>c</b>,<b>d</b>) Greater magnification of random and aligned fibers shows occasional adherence between fibers and overlapping/layering of fibers. Representative directionality histograms show no more than 2% of fibers sharing 1° of orientation in a random construct (<b>e</b>), whereas an aligned construct (<b>f</b>) had a strong peak, with 8% of fibers at peak orientation, with Gaussian distribution around this peak (insets show analyzed phase micrographs; scale bars: 50 µm). (<b>g</b>) Graph shows average fiber diameter (** <span class="html-italic">p</span> = 0.0063, unpaired two-tailed Mann–Whitney test, n = 40 (random) and 28 (aligned) fibers). (<b>h</b>) Random constructs show a wider distribution of fibers across orientations, illustrated by larger standard deviation (SD) around the most common orientation, vs. aligned constructs, which show small SD, i.e., narrow peak (compare with (<b>e</b>,<b>f</b>)). (<b>i</b>) Random constructs show few fibers at ‘peak’ direction, whereas aligned constructs show a greater percentage of fibers at peak orientation. For (<b>h</b>,<b>i</b>): *** <span class="html-italic">p </span> &lt; 0.0001, unpaired two-tailed Mann–Whitney test, n = 17 (random) and 22 (aligned) micrographs.</p>
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<p>Fluorescence micrographs of neural co-cultures on glass and PCL fibers. (<b>a</b>–<b>c</b>) Phase contrast micrographs comparing neural co-cultures on coverslips, then randomly oriented fibers, and aligned fibers. Counterpart micrographs in each column then show GFAP (<b>d</b>–<b>f</b>), GFAP-phase merge to indicate astrocyte association with fibers (<b>g</b>–<b>i</b>), Tuj1 (<b>j</b>–<b>l</b>), Tuj1-phase merge to indicate neuronal association with fibers (<b>m</b>–<b>o</b>), and GFAP-Tuj1-DAPI merge (<b>p</b>–<b>r</b>) to show nuclei (DAPI<sup>+</sup>). GFAP: glial fibrillary acidic protein, astrocyte marker; PCL: polycaprolactone; Tuj1: neuronal marker.</p>
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<p>Astrocytes and neurons on PCL fibers exhibited elongated morphologies. Box and whisker (10–90%) plots showing Feret’s diameter, aspect ratio, and process length, for GFAP<sup>+</sup> cells (green box) and Tuj1<sup>+</sup> cells (orange box). (<b>a</b>) Astrocyte Feret’s diameter was greater on aligned constructs (5- and 9DIV vs. coverslips). At 9DIV, it was also greater on randomly oriented constructs vs. coverslips. (<b>b</b>) Astrocyte aspect ratio (length/width) was greater on aligned constructs (vs. coverslips and random; 5- and 9DIV). (<b>c</b>) Average astrocyte process length was greater on fibers (aligned vs. coverslips, random vs. coverslips; 5- and 9DIV). All substrates showed greater process length at 9DIV vs. 5DIV. (<b>d</b>) Neuronal Feret’s diameter was greater on aligned constructs at 9DIV (vs. coverslips), but otherwise no differences were detected. (<b>e</b>) Neuronal aspect ratio was greater on aligned constructs (vs. coverslips and random) at 5DIV, but not at 9DIV. Average aspect ratio did not increase over time for any substrate. (<b>f</b>) Average neurite length was greater at 9DIV (vs. 5DIV) for coverslips and aligned constructs. It was also greater on aligned constructs vs. random at 9DIV. All stats: Kruskal–Wallis with Dunn’s post-tests; * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>Astrocyte and neuron elongation matched the orientation of aligned fiber constructs. Directionality histograms show even distribution of orientations in coverslip cultures for (<b>a</b>) phase contrast, (<b>b</b>) GFAP, and (<b>c</b>) Tuj1 micrographs, consistent with cells extending in all directions approximately equally. However, strong peaks of orientation were present in histograms for aligned fiber constructs, with the peak in (<b>d</b>) phase contrast micrographs (fibers) matching the peaks in counterpart channels for (<b>e</b>) GFAP and (<b>f</b>) Tuj1. (<b>g</b>) Taking peak direction of orientation (°) for phase contrast micrographs, and subtracting the peak orientation for GFAP counterpart micrographs, showed smaller differences for aligned constructs vs. coverslips and vs. randomly oriented fibers, at both 5- and 9DIV. (<b>h</b>) Tuj1 micrographs more closely matched fiber orientation in aligned constructs at 5DIV (vs. coverslips) and at 9DIV (vs. coverslips and random). (<b>a</b>–<b>f</b>) are representative histograms from counterpart micrographs. (<b>g</b>,<b>h</b>) * <span class="html-italic">p</span> &lt; 0.05; ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001; unpaired Kruskal–Wallis, Dunn’s post-test; n = 16, 16, 18, 10, 7, 5 individual image sets across cultures; plotted with log<sub>10</sub> <span class="html-italic">y</span>-axis, due to the wide spread of data points.</p>
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23 pages, 6407 KiB  
Article
Pull-Out Properties of Nano-Processed Para-Aramid Fabric Materials in Soft Ballistic: An Experimental Analysis
by Nedim Erman Bilisik, Gulhan Erdogan and Kadir Bilisik
Appl. Sci. 2025, 15(5), 2260; https://doi.org/10.3390/app15052260 - 20 Feb 2025
Viewed by 364
Abstract
Single and multiple pull-out properties of a nano-processed para-aramid fabric structure were investigated. The nano pull-out behavior exhibited three distinct regions, namely crimp extension, interlacement rupture, and stick-slip. Multiple yarn pull-out tests demonstrated a significantly higher pull-out force compared to single-yarn pull-out, primarily [...] Read more.
Single and multiple pull-out properties of a nano-processed para-aramid fabric structure were investigated. The nano pull-out behavior exhibited three distinct regions, namely crimp extension, interlacement rupture, and stick-slip. Multiple yarn pull-out tests demonstrated a significantly higher pull-out force compared to single-yarn pull-out, primarily attributed to the incorporation of nanoparticles. Furthermore, it was observed that an increase in fabric length resulted in an approximately linear increase in both yarn crimp extension and pull-out force. The highest pull-out force was obtained in the nano-hexagonal boron carbide (nh-B4C, 0.3%) para-aramid structure, followed by multiwalled carbon nanotube (MWCNT, 0.3%) para-aramids. This is because of the enhancement of filament-to-filament friction, especially in the interlacement zone of fabric, alongside the cumulative frictional interactions among the nanoparticles. Additionally, the findings highlight an improvement in crimp extension energy absorption facilitated by nanoparticle incorporation in soft fabric. Notably, the improvement in the energy absorption capacity of yarns within the fabric, without disintegration, is considered significant at this stage. These results indicate a promising potential for performance enhancement in prospective soft ballistic applications. Full article
(This article belongs to the Special Issue Advances in Nanomaterials and Their Applications)
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Figure 1

Figure 1
<p>(<b>a</b>) Optical microscope image of para-aramid fabric (OM, magnification 6.7×). (<b>b</b>) Field emission scanning electron microscope (FESEM) images of nano B<sub>4</sub>C (scale: 200 nm; magnification: 20,000×). (<b>c</b>) MWCNTs (scale: 200 nm; magnification: 30,000×); (<b>d</b>) GNPs (scale: 200 nm; magnification: 20,000×).</p>
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<p>Processing route (iterative compression method) of developed various nanocoated p-aramid structures (digital camera).</p>
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<p>Pull-out samples and testing for various nanocoated p-aramid fabric structures. (<b>a</b>) Nano B<sub>4</sub>C coated p-aramid fabric. (<b>b</b>) Pull-out sample of nano B<sub>4</sub>C fabric. (<b>c</b>) Pull-out sample of MWCNT fabric. (<b>d</b>) Pull-out sample of GNP fabric. (<b>e</b>) Pull-out sample of control fabric. (<b>f1</b>) Single-yarn and (<b>f2</b>) multiple-yarn pull-out in nano B<sub>4</sub>C fabric. (<b>g1</b>) Single-yarn and (<b>g2</b>) multiple-yarn pull-out in MWCNT fabric. (<b>h1</b>) Single-yarn and (<b>h2</b>) multiple-yarn pull-out in GNP fabric. (<b>i1</b>) Single-yarn and (<b>i2</b>) multiple-yarn pull-out in control fabric. (<b>j</b>) Pull-out fabric dimensions, schematic (digital camera).</p>
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<p>Surface morphology of various nanocoated p-aramid fabric structures. (<b>a1</b>) Nano B<sub>4</sub>C-coated plain fabric surface (OM, magnification 6.7×). (<b>a2</b>,<b>a3</b>) Nano B<sub>4</sub>C-coated fabric and filament surfaces (SEM, 35×, 2000×, respectively). (<b>a4</b>) Magnified (SEM, 10,000×) view of nano B<sub>4</sub>C on the filament surface. (<b>b1</b>) MWCNT-coated fabric surface (OM, 6.7×). (<b>b2</b>,<b>b3</b>) Surface of MWCNT-coated fabric (SEM 35×, 2000×, respectively). (<b>b4</b>) Magnified (SEM, 10,000×) view of MWCNTs on the filament surface. (<b>c1</b>) GNP-coated fabric surface (OM, 6.7×). (<b>c2</b>,<b>c3</b>) GNP-coated fabric surface (SEM, 35×, 2000×, respectively). (<b>c4</b>) Magnified (SEM, 10,000×) view of GNPs on the filament surface. (<b>d1</b>) Control fabric surface (OM, 6.7×). (<b>d2</b>,<b>d3</b>) Control fabric surface (SEM, 35×, 300×, respectively).</p>
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<p>General characterization of the pull-out force (N)–displacement (mm) graphs for nanocoated p-aramid fabric structure (single yarn, n-B<sub>4</sub>C-coated).</p>
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<p>Single-yarn and multiple-yarn (2 ends and 3 ends) consecutive pull-out force (N)–displacement (mm) graphs for nanocoated p-aramid fabric structures. (<b>a1</b>,<b>b1</b>,<b>c1</b>) Nanocoated B<sub>4</sub>C p-aramid fabric (BPO). (<b>a2</b>,<b>b2</b>,<b>c2</b>) MWCNT-coated p-aramid fabric (MPO). (<b>a3</b>,<b>b3</b>,<b>c3</b>) GNP-coated p-aramid fabric. (<b>a4</b>,<b>b4</b>,<b>c4</b>) Control fabric (KPO).</p>
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<p>Single and multiple (two yarns and three yarns) crimp extensions and pull-out forces corresponding to the fabric lengths for nanocoated p-aramid fabric structures. (<b>a</b>) Single-yarn crimp extension pull-out forces. (<b>b</b>) Two-yarn crimp extension pull-out forces. (<b>c</b>) Three-yarn crimp extension pull-out forces.</p>
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<p>Single- and multiple (two ends and three end)-yarn maximum pull-out force–displacement graph for nanocoated p-aramid fabric structures. (<b>a</b>) Single-yarn maximum pull-out forces. (<b>b</b>) Two-yarn pull-out forces. (<b>c</b>) Three-yarn pull-out forces. (<b>d</b>) Tensile strength of single various nanocoated para-aramid yarns.</p>
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<p>Single- and multiple (two ends and three ends)-yarn intra-yarn shear strengths for various nanocoated p-aramid fabric structures.</p>
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<p>Determination of the representative energy stages from the pull-out displacement graph of the nano B<sub>4</sub>C-coated p-aramid fabric.</p>
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<p>Single and multiple (two yarns and three yarns) pull-out energy results of nanocoated p-aramid fabric structures. (<b>a</b>) Single-yarn pull-out energy. (<b>b</b>) Two-end pull-out energy. (<b>c</b>) Three-end pull-out energy.</p>
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29 pages, 10857 KiB  
Article
Improved Mechanical and Thermal Properties of Date Palm Microfiber-Reinforced PCL Biocomposites for Rigid Packaging
by Sakib Hossain Khan, Hom N. Dhakal, Abu Saifullah and Zhongyi Zhang
Molecules 2025, 30(4), 857; https://doi.org/10.3390/molecules30040857 - 13 Feb 2025
Viewed by 654
Abstract
To increase the use of agricultural residues, such as date palm fibers, for the sustainable reinforcement of biocomposites, this study investigated the incorporation of varying weight percentages of date palm microfibers (DPMF) ranging from 0 wt.% to 10 wt.% into polycaprolactone (PCL) matrix. [...] Read more.
To increase the use of agricultural residues, such as date palm fibers, for the sustainable reinforcement of biocomposites, this study investigated the incorporation of varying weight percentages of date palm microfibers (DPMF) ranging from 0 wt.% to 10 wt.% into polycaprolactone (PCL) matrix. Biocomposites were fabricated using a combination of compression molding and dry blending techniques with and without sodium hydroxide (NaOH) alkali treatment. The surface modification was found to increase the surface roughness of the fibers, removing impurities such as lignin, hemicellulose, and wax, while improving crystallinity, as evidenced by FTIR, XRD, TGA, and particle size analyses. Among the different biocomposites investigated, the results for 5 wt.% DPMF content biocomposites exhibited the highest tensile properties: approximately 20% increase in tensile strength and 164% increase in Young’s Modulus in comparison to neat PCL. The crystallinity of the matrix exhibited an increasing trend from approximately 39% for neat PCL to 43% for the 5 wt.% DPMF biocomposites. Furthermore, treated biocomposites demonstrated higher water-repellency behavior and improved thermal properties. Dynamic mechanical analysis (DMA) results indicated enhanced storage moduli for alkali-treated composites; at 35 °C, the storage modulus showed approximately 22% increase compared to the untreated DPMF biocomposites, reflecting improved stiffness and thermomechanical performances. This study highlights the potential of DPMF as an efficient, eco-friendly alternative to fossil-based conventional reinforcement for biocomposite materials’ potential for sustainable rigid packaging applications. Full article
(This article belongs to the Topic Biomass for Energy, Chemicals and Materials)
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Graphical abstract

Graphical abstract
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<p>Steps involved in extraction of cellulosic materials from agricultural residues.</p>
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<p>Suitability of DPMFs and PCL in packaging application.</p>
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<p>Dry blending–compression molding benefits.</p>
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<p>Fiber-grinding process: (<b>a</b>) date palm leaf fibers; (<b>b</b>) RETSCH Ultra Centrifugal Mill ZM 300; (<b>c</b>) date palm micro-fibers.</p>
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<p>Description of dry-blending process used for biocomposites fabrication: (<b>a</b>) polymer grinding; (<b>b</b>) shear mixing of fibers and polymer; (<b>c</b>) compression molding; (<b>d</b>) final biocomposites plates.</p>
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<p>The neat PCL and different concentrations of DPMF composites where the samples became darker with the increase in micro-fiber content compared to the neat PCL.</p>
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<p>FTIR spectra for untreated and treated DP microfibers.</p>
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<p>X-ray diffraction (XRD) spectra of untreated and treated DP microfibers.</p>
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<p>Crystallinity index versus NaOH concentration for agave fibers [<a href="#B44-molecules-30-00857" class="html-bibr">44</a>] (Copyright License number: 5956470259977).</p>
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<p>Thermogravimetric Analysis (TGA): (<b>a</b>) weight loss versus temperature traces; (<b>b</b>) derivative thermogravimetric (DTG) of untreated and alkali-treated date palm microfibers.</p>
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<p>Cumulative distribution of the particle size of the untreated and treated date palm micro-fibers.</p>
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<p>Optical microscopy images (<b>a</b>,<b>b</b>) untreated microfiber; (<b>c</b>,<b>d</b>) treated micro-fiber.</p>
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<p>(<b>a</b>) Tensile strength and (<b>b</b>) Young’s Modulus of the untreated and treated date palm–PCL biocomposites.</p>
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<p>(<b>a</b>) Flexural strength and (<b>b</b>) flexural modulus of the untreated and treated date palm microfiber–PCL biocomposites.</p>
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<p>X-ray μCT micrographs of (<b>a</b>) 2.5 wt.%, (<b>b</b>) 5 wt.%, and (<b>c</b>) 10 wt.% date palm microfiber-reinforced PCL composites.</p>
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<p>Moisture absorption curves (<b>a</b>) for 10% and 5% with respect to time; (<b>b</b>) moisture absorption of all samples.</p>
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<p>DSC heating curves (<b>a</b>) for neat PCL with 5 and 10% DPF-PCL composite samples (<b>b</b>) for treated and untreated DPMF composite samples.</p>
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<p>(<b>a</b>) Storage modulus curve for neat PCL and different DPMF composites; (<b>b</b>) storage modulus for treated and untreated DPMF composites.</p>
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<p>(<b>a</b>) Viscosity with respect to frequency; (<b>b</b>) viscosity with respect to shear rate; (<b>c</b>) storage modulus; (<b>d</b>) loss modulus with respect to frequency.</p>
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<p>Curves of viscosity versus shear rate for alkali-treated DPF and untreated DPF.</p>
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<p>TGA of 5% and 10% treated DPMF-PCL biocomposites.</p>
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<p>SEM images of fractured region; (<b>a</b>,<b>b</b>) untreated date palm fiber composites; (<b>c</b>–<b>f</b>) treated date palm fiber composites.</p>
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12 pages, 3641 KiB  
Article
Microplastics in Urban Bird Feces: A Methodological Approach and Case Study in Mexico City
by Victoria Amellalli Vazquez-Cruz, Alethia Vázquez-Morillas, Arely Areanely Cruz-Salas, Ana Isabel Hernández-Soriano, Getsemaní Cervantes-Cabrera, Mariana Elizabeth Ballesteros-López and Juan Carlos Alvarez-Zeferino
Microplastics 2025, 4(1), 6; https://doi.org/10.3390/microplastics4010006 - 5 Feb 2025
Viewed by 520
Abstract
Microplastics (MP) are ubiquitous contaminants in diverse environmental matrices, including biota. Urban birds, such as pigeons (Columba livia), are particularly vulnerable to MP exposure due to their scavenging habits and proximity to human activities. This study developed and applied a methodology [...] Read more.
Microplastics (MP) are ubiquitous contaminants in diverse environmental matrices, including biota. Urban birds, such as pigeons (Columba livia), are particularly vulnerable to MP exposure due to their scavenging habits and proximity to human activities. This study developed and applied a methodology to assess MP presence in pigeon feces, starting with a review of existing methods for extracting MPs from organic matrices. Of all the methodologies investigated, a method was established to be tested, varying the reagent, using pigeon feces collected from the Universidad Autónoma Metropolitana, Azcapotzalco Unit (UAM-A) and 15 virgin microplastics of five different types. Of both reagents, it was found that the method with 50% H2O2 presented better results (degradation of almost all organic matter and recovery efficiency of 93.33%). The selected method was optimized before being applied to feces collected from three sites in Mexico City (n = 10 samples per site). MPs were extracted using a digestion process with 50% hydrogen peroxide, flotation test with CaCl2, staining with red Nile dye and vacuum filtration and analyzed by microscopy and FTIR. Concentrations ranged from 16.4 to 27.8 MP/g dry feces, with fragments (80%) and fibers (20%) being the predominant shapes. The most common colors were black (32%) and white (22%), the polymers identified included polystyrene and polyethylene and the most common size was < 1 mm (54%). These findings suggest that pigeons ingest MP during feeding, likely due to confusion with organic matter, highlighting the risks of urban plastic pollution to avian health. The ingestion of MPs could lead to malnutrition, organ damage, and ecosystem imbalances, underscoring the need for improved waste management in urban areas. This study provides evidence of the pervasive impact of plastic pollution in non-marine environments, demonstrating the potential of urban birds as bio-indicators of local contamination. Full article
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<p>(<b>a</b>) Site 1—truck parking; (<b>b</b>) Site 2—houses; (<b>c</b>) Site 3—train workshop.</p>
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<p>Box-and-whisker diagram of the three sampled sites. Red dots inside the boxes show the average.</p>
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<p>Classification of microplastics: (<b>a</b>) color, (<b>b</b>) shape, (<b>c</b>) polymer and (<b>d</b>) size in millimeters.</p>
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<p>Classification of microplastics: (<b>a</b>) color, (<b>b</b>) shape, (<b>c</b>) polymer and (<b>d</b>) size in millimeters.</p>
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<p>Examples of microplastics (circled in yellow) extracted from pigeon feces.</p>
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27 pages, 30466 KiB  
Article
Electrospun Membranes Loaded with Melanin Derived from Pecan Nutshell (Carya illinoinensis) Residues for Skin-Care Applications
by Michell García-García, Jesús Salvador Jaime-Ferrer, Fernanda Nayeli Medrano-Lango, Elizabeth Quintana-Rodríguez, Tonatiu Campos-García, Erika Rodríguez-Sevilla and Domancar Orona-Tamayo
Membranes 2025, 15(2), 44; https://doi.org/10.3390/membranes15020044 - 3 Feb 2025
Viewed by 1180
Abstract
This study investigates the incorporation of melanin extracted from pecan nutshell residues into a polyacrylonitrile (PAN) matrix during the electrospinning of microfiber membranes. Melanin concentrations of 0.5, 2.0, and 5.0% w/w were incorporated to enhance the physicochemical and biological properties of [...] Read more.
This study investigates the incorporation of melanin extracted from pecan nutshell residues into a polyacrylonitrile (PAN) matrix during the electrospinning of microfiber membranes. Melanin concentrations of 0.5, 2.0, and 5.0% w/w were incorporated to enhance the physicochemical and biological properties of the fibers. The melanin-loaded PAN fibers exhibited significant antioxidant activity against DPPH and ABTS radicals, with scavenging rates ranging from 46.58% to 62.77% and 41.02% to 82.36%, respectively, while unmodified PAN fibers showed no activity. Furthermore, the melanin-loaded membranes demonstrated antimicrobial effects. The membranes also exhibited an important enzyme inhibition activity against collagenase (37%), hyaluronidase (22%), tyrosinase (36%), and elastase (33%). Molecular docking studies reveal different potential amino acids of the active sites of aging enzymes that interact strongly with melanin pigment, particularly collagenase, followed by hyaluronidase, tyrosinase, and elastase. These results suggest that the novel melanin-loaded PAN membranes possess promising bioactive properties with potential applications in different skin-care applications. Full article
(This article belongs to the Special Issue Recent Advances in Polymeric Membranes—Preparation and Applications)
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<p>Fibers composed of polyacrylonitrile (PAN) and melanin pigment. (<b>A</b>) Control (PAN), (<b>B</b>) PAN + 0.5% of melanin (PM0.5), (<b>C</b>) PAN + 2.0% of melanin (PM2.0), and (<b>D</b>) PAN + 5.0% of melanin (PM5.0).</p>
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<p>Light microscopy images of fiber membranes composed by PAN and melanin pigment. (<b>A</b>) Control (PAN), (<b>B</b>) PAN + 0.5% of melanin (PM0.5), (<b>C</b>) PAN + 2.0% of melanin (PM2.0), and (<b>D</b>) PAN + 5.0% of melanin (PM5.0).</p>
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<p>SEM micrographs of fiber composed by PAN and melanin pigment. (<b>A</b>) Control (PAN), (<b>B</b>) PAN + 0.5% of melanin (PM0.5), (<b>C</b>) PAN + 2.0% of melanin (PM2.0), and (<b>D</b>) PAN + 5.0% of melanin (PM5.0) and diameter size distribution histogram of samples labeled as (<b>E</b>–<b>H</b>), respectively, <math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>100</mn> </mrow> </semantics></math>.</p>
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<p>Infrared spectra (FTIR) within a wavenumber range of 4000 cm<sup>−1</sup> to 500 cm<sup>−1</sup> of melanin from nutshell and membranes obtained with melanin pigment, PAN control, PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0) fibers.</p>
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<p>Degree of swelling of electrospun membranes composed of PAN and melanin pigment. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Bars represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>3</mn> </mrow> </semantics></math>) of the water uptake in %. Different letters indicate significant differences between all factor combinations (univariate ANOVA after post hoc Tukey test, <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Contact angle of electrospun membranes composed of PAN and melanin pigment. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Bars represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>10</mn> </mrow> </semantics></math>) of the contact angle in degrees. Different letters indicate significant differences between all factor combinations (univariate ANOVA after post hoc Tukey test, <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>PAN and PAN–melanin fiber degradations for two weeks. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Bars represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>3</mn> </mrow> </semantics></math>) of the fiber degradation in %. Different letters indicate significant differences between all factor combinations (univariate ANOVA after post hoc Tukey test, <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>The in vitro release profiles of melanin from different PAN and PAN–melanin fibers over time. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Points represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>3</mn> </mrow> </semantics></math>) of the melanin liberation from fibers.</p>
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<p>Analysis of mechanical properties of the different produced membranes, (<b>A</b>) tensile strength (MPa), (<b>B</b>) rupture strength (%), and (<b>C</b>) Young’s modulus (MPa) in PAN electrospun membranes in vertical and horizontal direction. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Bars represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>5</mn> </mrow> </semantics></math>) for all physical properties. Different letters indicate significant differences between all factor combinations (univariate ANOVA after post hoc Tukey test, <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Free radical scavenging activity of melanin membranes against DPPH and ABTS. Control (PAN), PAN + 0.5% of melanin (PM0.5), PAN + 2.0% of melanin (PM2.0), and PAN + 5.0% of melanin (PM5.0). Bars represent means ± SE (<math display="inline"><semantics> <mrow> <mi>n</mi> <mo>=</mo> <mn>3</mn> </mrow> </semantics></math>) for radical scavenging in %. Different letters indicate significant differences between all factor combinations (univariate ANOVA after post hoc Tukey test, <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>Tridimensional structure of the molecular docking between melanin pigment and the catalytic sites of various aging-related enzymes. Surface (<b>A</b>–<b>D</b>) and cartoon (<b>E</b>–<b>H</b>) representations of the predicted models illustrate interactions between melanin and the enzymes: collagenase (<b>A</b>,<b>E</b>), hyaluronidase (<b>B</b>,<b>F</b>), elastase (<b>C</b>,<b>G</b>), and tyrosinase (<b>D</b>,<b>H</b>). The surface models depict the most accurate predictions, while the cartoon representations highlight the amino acids (pink) involved in the protein–ligand interactions within the enzyme binding pocket and melanin (green). In (<b>E</b>), green and gray dots represent calcium (Ca) and zinc (Zn) atoms, respectively. Brown dots in (<b>H</b>) depict copper (Cu) atoms.</p>
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15 pages, 2373 KiB  
Article
Characterization of Structure and Morphology of Cellulose Lyocell Microfibers Extracted from PAN Matrix
by Igor Makarov, Ekaterina Palchikova, Markel Vinogradov, Yaroslav Golubev, Sergey Legkov, Petr Gromovykh, Georgy Makarov, Natalia Arkharova, Denis Karimov and Radmir Gainutdinov
Polysaccharides 2025, 6(1), 10; https://doi.org/10.3390/polysaccharides6010010 - 3 Feb 2025
Viewed by 620
Abstract
Polymer matrices can be reinforced with cellulose fillers in a variety of geometric shapes. Depending on the morphology of the particles, the volume fraction of the composite additive may decrease, while the values of the elastic modulus may increase. Increasing the length while [...] Read more.
Polymer matrices can be reinforced with cellulose fillers in a variety of geometric shapes. Depending on the morphology of the particles, the volume fraction of the composite additive may decrease, while the values of the elastic modulus may increase. Increasing the length while decreasing the width of the cellulose filler is an intriguing path in the development of composite additives and materials based on it. It is difficult to form thin continuous cellulose fibers, but this can be accomplished via the sea-island composite fiber manufacturing process. The creation of cellulose fibrils in polyacrylonitrile (PAN)/cellulose based systems happens during the spinning of the mixed solution. A selective solvent facilitates the isolation of cellulose fibrils. The structure of the isolated microfibers was investigated using X-ray diffraction, IR spectroscopy, SEM, and AFM. The structure of the resulting cellulose microfibers was compared to bacterial cellulose. It has been shown that composite fibers have a superposition pattern, while cellulose fibrils have a structure different from native cellulose and similar to Lyocell fibers (polymorph II). The crystallite sizes and crystallinity of regenerated cellulose were determined. The identified structural parameters for cellulose fibrils provide strength at the level of industrial hydrated cellulose fibers. Full article
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<p>Photograph of 70% PAN-30% cellulose fiber washed from NMMO (<b>a</b>) and photograph of isolated cellulose microfiber skein (<b>b</b>).</p>
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<p>Photographs of cellulose fibers in transmitted light (<b>a</b>) and crossed polaroids (<b>b</b>).</p>
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<p>SEM images of cellulose microfibers (<b>a</b>–<b>c</b>) and bacterial cellulose (<b>d</b>–<b>f</b>). The bunch of parallel microfibers and separate microfiber are marked with arrows (<b>b</b>).</p>
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<p>IR spectra of Lyocell fibers (a), composite fibers (70% PAN-30% cellulose) (b), microfibers (c), bacterial cellulose (d), and PAN (e).</p>
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<p>Diffraction patterns of PAN powder (a), bacterial cellulose (b), and isolated microfibers (c).</p>
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<p>Topographic map of cellulose microfibers (<b>a</b>) and bacterial cellulose (<b>b</b>).</p>
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16 pages, 4100 KiB  
Article
Cellulose-Based Composite Materials for Fresh Water Extraction from Atmospheric Air
by Dmitry Repin, Mariia Gablina, Natalya Repina, Kirill Cherednichenko, Wenpeng Li, Yuliiya Gushchina, Evgenii Ivanov, Vyacheslav Melnikov, Rawil Fakhrullin and Vladimir Vinokurov
Polymers 2025, 17(3), 328; https://doi.org/10.3390/polym17030328 - 25 Jan 2025
Viewed by 259
Abstract
The fibrous hybrid material was synthesized by suspension radical styrene polymerization on the surface of cellulose microfibers. The resulting material was used to prepare a thermally stable and mechanically strong porous composite matrix that was employed as a carrier for further precipitation of [...] Read more.
The fibrous hybrid material was synthesized by suspension radical styrene polymerization on the surface of cellulose microfibers. The resulting material was used to prepare a thermally stable and mechanically strong porous composite matrix that was employed as a carrier for further precipitation of the hygroscopic agents: CaCl2 and 1-butyl-3-methylimidazolium chloride. The obtained composite materials were used to capture atmospheric water at different relative humidity levels and extract fresh water. A composite material containing an ionic liquid (1-butyl-3-methylimidazolium chloride) as a hygroscopic agent demonstrated the best water absorption efficiency and reusability potential. Full article
(This article belongs to the Special Issue Multifunctional Polymer Composite Materials)
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<p>The scheme of synthesis of MFC/PS hybrid fibrils and composite porous matrix. The obtained MFC/PS hybrid fibrils during the first stage were compacted in a piston-cylinder with the addition of a small amount of acetone.</p>
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<p>The scheme of water absorption experiment. The sample of pristine (or modified) MFC/PS matrix was placed under a transparent cover over a container of water at constant humidity (φ = 28%, 63%) and temperature. The weight of the sample was measured every 10 min.</p>
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<p>SEM micrographs of bare MFC (<b>a</b>), MFC/PS hybrid fibrils (<b>b</b>), MFC/PS pristine porous composite matrix (<b>c</b>), MFC/PS/CC (<b>d</b>), MFC/PS/BMIMCl (<b>e</b>).</p>
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<p>FTIR spectra of MFC/PS, MFC/PS/CC, and MFC/PS/BMIMCl. The wavenumbers of PS and BMIMCl characteristic bands are underwritten.</p>
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<p>TGA and dTGA curves of (<b>A</b>,<b>C</b>) MFC, PS, MFC/PS, (<b>B</b>,<b>D</b>) MFC/PS, MFC/PS/CC, and MFC/PS/BMIMCl. The corresponding dTGA peaks are underwritten.</p>
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<p>Compressive strength performance of pristine and modified MFC/PS matrices: (<b>a</b>) tensile strength, (<b>b</b>) tensile load.</p>
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<p>(<b>a</b>) Sorption of MFC/PS porous matrix immersed in water; (<b>b</b>) desorption at different temperatures; (<b>c</b>) demonstration of MFC/PS porous matrix shape stability after 10 sorption/desorption cycles under load of 16 kg.</p>
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<p>Moisture absorption from the air by pristine MFC/PS, MFC/PS/BMIMCl, and MFC/PS/CC at (<b>a</b>) low (28%) and (<b>b</b>) high (63%) humidity and 25 °C; (<b>c</b>) desorption curves of pristine MFC/PS, MFC/PS/BMIMCl, MFC/PS/CC at 55 °C and humidity of 8%.</p>
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25 pages, 17433 KiB  
Article
Silicone Composites with Electrically Oriented Boron Nitride Platelets and Carbon Microfibers for Thermal Management of Electronics
by Romeo Cristian Ciobanu, Magdalena Aflori, Cristina Mihaela Scheiner, Mihaela Aradoaei and Dorel Buncianu
Polymers 2025, 17(2), 204; https://doi.org/10.3390/polym17020204 - 15 Jan 2025
Viewed by 459
Abstract
This study investigated silicone composites with distributed boron nitride platelets and carbon microfibers that are oriented electrically. The process involved homogenizing and dispersing nano/microparticles in the liquid polymer, aligning the particles with DC and AC electric fields, and curing the composite with IR [...] Read more.
This study investigated silicone composites with distributed boron nitride platelets and carbon microfibers that are oriented electrically. The process involved homogenizing and dispersing nano/microparticles in the liquid polymer, aligning the particles with DC and AC electric fields, and curing the composite with IR radiation to trap particles within chains. This innovative concept utilized two fields to align particles, improving the even distribution of carbon microfibers among BN in the chains. Based on SEM images, the chains are uniformly distributed on the surface of the sample, fully formed and mature, but their architecture critically depends on composition. The physical and electrical characteristics of composites were extensively studied with regard to the composition and orientation of particles. The higher the concentration of BN platelets, the greater the enhancement of dielectric permittivity, but the effect decreases gradually after reaching a concentration of 15%. The impact of incorporating carbon microfibers into the dielectric permittivity of composites is clearly beneficial, especially when the BN content surpasses 12%. Thermal conductivity showed a significant improvement in all samples with aligned particles, regardless of their composition. For homogeneous materials, the thermal conductivity is significantly enhanced by the inclusion of carbon microfibers, particularly when the boron nitride content exceeds 12%. The biggest increase happened when carbon microfibers were added at a rate of 2%, while the BN content surpassed 15.5%. The thermal conductivity of composites is greatly improved by adding carbon microfibers when oriented particles are present, even at BN content over 12%. When the BN content surpasses 15.5%, the effect diminishes as the fibers within chains are only partly vertically oriented, with BN platelets prioritizing vertical alignment. The outcomes of this study showed improved results for composites with BN platelets and carbon microfibers compared to prior findings in the literature, all while utilizing a more straightforward approach for processing the polymer matrix and aligning particles. In contrast to current technologies, utilizing homologous materials with uniformly dispersed particles, the presented technology reduces ingredient consumption by 5–10 times due to the arrangement in chains, which enhances heat transfer efficiency in the desired direction. The present technology can be used in a variety of industrial settings, accommodating different ingredients and film thicknesses, and can be customized for various applications in electronics thermal management. Full article
(This article belongs to the Special Issue Electrical Properties of Polymer Composites)
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<p>Orientation process of composites containing BN platelets.</p>
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<p>Laboratory tape caster equipment: (<b>a</b>) setup assembly; (<b>b</b>) adjustable electrodes area; (<b>c</b>) IR curing area; (<b>d</b>) curing temperature control panel.</p>
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<p>BN platelets before and after integration into composites with uniformly distributed particles.</p>
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<p>Internal structure of composite R1, with 12% BN platelet (uniformly distributed particles).</p>
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<p>Internal structure of composite R2, with 12% BN platelet (oriented particles, aligned along a chain).</p>
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<p>SEM images for sample R3.</p>
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<p>SEM images for sample R4.</p>
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<p>SEM images for sample R5.</p>
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<p>SEM images for sample R6.</p>
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<p>SEM images for sample R9.</p>
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<p>SEM images for sample R10.</p>
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<p>Comparative SEM images for samples: (<b>a</b>) R11 and (<b>b</b>) R12.</p>
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<p>Comparative XRD analysis for samples (<b>a</b>) R1 and (<b>b</b>) R2.</p>
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<p>Comparative XRD analysis for samples (<b>a</b>) R5 and (<b>b</b>) R6.</p>
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<p>EDX results for R3.</p>
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<p>EDX results for R5.</p>
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<p>Dielectric permittivity characteristics of composites with uniform dispersion.</p>
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<p>Dielectric permittivity characteristics of composites with oriented particles.</p>
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<p>Thermal conductivity characteristics of composites with uniform dispersion.</p>
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<p>Thermal conductivity characteristics of composites with oriented particles.</p>
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10 pages, 1925 KiB  
Article
Comparison of Lichen and Moss Transplants for Monitoring the Deposition of Airborne Microfibers
by Lisa Grifoni, Mehriban Jafarova, Noelia S. La Colla, Julian Aherne, Alessio Raulli and Stefano Loppi
Sustainability 2025, 17(2), 537; https://doi.org/10.3390/su17020537 - 12 Jan 2025
Viewed by 707
Abstract
Interest in using lichens and mosses to monitor airborne microplastics is growing, but few studies have thoroughly compared their effectiveness as biomonitors. Here, we directly compare the ability of lichen and moss transplants collected from a rural area to accumulate microfibers (MFs) and [...] Read more.
Interest in using lichens and mosses to monitor airborne microplastics is growing, but few studies have thoroughly compared their effectiveness as biomonitors. Here, we directly compare the ability of lichen and moss transplants collected from a rural area to accumulate microfibers (MFs) and Potentially Toxic Elements (PTEs) under the same deployment conditions. Transplants (n = 60; triplicates for both lichen and moss) were co-deployed on tree branches across a range of urban exposure sites (e.g., commercial and residential areas and urban parks) for 77 days in Siena, Italy. The results showed that both biomonitors accumulated similar amounts of MFs, in terms of counts and on a mass basis, but when expressed on a surface area basis, lichens showed significantly higher values. Irrespective of the metric, lichen and moss MF accumulation data were strongly correlated. In contrast, there was no correlation between MFs and PTEs, suggesting that their sources were different. MFs accumulated by lichen and moss transplants were dominated by polyethylene terephthalate (PET) and polypropylene polymers, suggesting that the main source of airborne MFs is synthetic textiles. Our results suggest that both lichen and moss transplants can be effectively used as low-cost monitors of atmospheric MFs in urban areas in support of the sustainable development goal of clean air. Full article
(This article belongs to the Special Issue Microplastic Research and Environmental Sustainability)
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<p>(<b>A</b>) Location of the province of Siena, Central Italy. (<b>B</b>) Deployment sites (<span class="html-italic">n</span> = 10) for lichen and moss transplants across the city of Siena with coordinates (latitude and longitude in decimal degrees).</p>
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<p>Images of MFs extracted from moss (<b>A</b>) and lichen (<b>B</b>) transplants.</p>
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<p>Correlation (Spearman’s R) between the number of MFs accumulated (count) by the lichen and moss at the 10 study sites (<a href="#sustainability-17-00537-t001" class="html-table">Table 1</a>).</p>
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<p>Proportion (%) of microfiber polymer types accumulated by the moss (<b>A</b>) and lichen (<b>B</b>) samples.</p>
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25 pages, 11243 KiB  
Article
Comparison of the Influence of Polypropylene (PP) or Polybutylene Terephthalate (PBT)-Based Meltblown and Polyester/Polyamide-Based Hydroentangled Inner Layers on the Sound and Thermal Insulation Properties of Layered Nonwoven Composite Structures
by Emel Çinçik, Süreyya Kocatepe and Eda Aslan
Polymers 2025, 17(1), 101; https://doi.org/10.3390/polym17010101 - 2 Jan 2025
Viewed by 602
Abstract
Thermal and sound insulation play a vital role in today’s world, and nonwoven composite structures including microfiber layers provide efficient solutions for addressing these demands. In this study, the sound and thermal insulation properties of nonwoven composite structures, including single-layer meltblown, multilayer meltblown, [...] Read more.
Thermal and sound insulation play a vital role in today’s world, and nonwoven composite structures including microfiber layers provide efficient solutions for addressing these demands. In this study, the sound and thermal insulation properties of nonwoven composite structures, including single-layer meltblown, multilayer meltblown, hydroentangled, and nanofiber nonwoven inner layers, were compared statistically by using Design Expert 13 software. The inner layer type and outer layer type of the composite structures were considered as independent variables, and thickness, bulk density, air permeability, sound absorption coefficient, and thermal resistance of composite structures were evaluated as dependent variables during statistical analyses. The effects of layer types on dependent variables were investigated comparatively, and the best inner and outer layers for high sound and thermal insulation were determined. It was concluded that the developed nonwoven composites including hydroentangled and three-layered meltblown layers demonstrated superior sound absorption properties at low (changing between 48% and 70%) and moderate (ranging between 77% and 96%) sound frequencies, respectively, when compared to composites and materials including single-layer meltblown or nanofiber nonwoven structures reported in prior studies. Additionally, it can be inferred that the composite structures obtained in this study exhibited thermal resistance properties (0.49 to 0.73 m2K/W) comparable to those of commercial thermal insulation materials. Full article
(This article belongs to the Section Polymer Applications)
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<p>The fibers constituting the thermally bonded outer layer.</p>
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<p>Variation in composite thickness with internal and external layer type.</p>
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<p>Variation in composite bulk density with internal and external layer type.</p>
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<p>Relation between inner layer and outer layer type and air permeability of nonwoven composite structures.</p>
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<p>Surface visualization of external layers composed of various fibers (3×).</p>
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<p>Relation between sound frequency and composite sound absorption coefficient by inner layer type, for composites including 7DH outer layer.</p>
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<p>Analysis of noise reduction properties for various nonwoven composite structures across distinct sound frequency ranges.</p>
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<p>Variation in thermal resistance of the composites by outer and inner layer type.</p>
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17 pages, 6327 KiB  
Article
Enhanced Mechanical and Acoustic Properties of Basalt Fiber/Polyurethane Composites by Silane Coupling Agents
by Mengchen Ge, Xiaodong Li, Fei Han, Xing Su, Hao Jiang, Youhao Liu, Yangwei Wang and Meishuai Zou
Polymers 2025, 17(1), 61; https://doi.org/10.3390/polym17010061 - 29 Dec 2024
Viewed by 790
Abstract
Modified basalt microfiber-reinforced polyurethane elastomer composites were prepared by a semi-prepolymer method with two different silane coupling agents (KH550 and KH560) in this study. Infrared spectroscopy was used to quantify the degree of microphase separation and analyze the formation of hydrogen bonding in [...] Read more.
Modified basalt microfiber-reinforced polyurethane elastomer composites were prepared by a semi-prepolymer method with two different silane coupling agents (KH550 and KH560) in this study. Infrared spectroscopy was used to quantify the degree of microphase separation and analyze the formation of hydrogen bonding in polyurethane. The interfacial surface and the morphology of fibers and composites from tensile fracture were examined by a scanning electron microscope. Further measurements were performed on an electronic universal testing machine for characterizing the mechanical properties of composites. Moreover, the loss factor and transmission loss of composite materials were obtained from dynamic thermomechanical analysis and acoustic impedance tube, respectively. The suitable concentrations in the modification of basalt fibers were established at 1% for KH550 and 1.5% for KH560. The best overall performance was obtained in KH550-BMF/PUE group, as the properties increased by 31% in tensile strength, 37% in elongation at break, and 21% in acoustic insulation. Full article
(This article belongs to the Special Issue Processing, Characterization and Modeling of Polymer Nanocomposites)
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<p>FTIR spectrum of basalt microfibers and modified basalt microfibers.</p>
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<p>FTIR spectrum of uncoated BMF/PUE and modified BMF/PUE composites.</p>
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<p>FTIR spectra of the carbonyl part of KH550-B4/PUE composites and Gauss–Lorentz peak splitting results.</p>
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<p>FTIR spectra of the carbonyl part of KH560-B4/PUE composites and Gauss–Lorentz peak splitting results.</p>
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<p>Stress–strain curves of PUE matrix and different composites with (<b>a</b>) KH550-B3/PUE and (<b>b</b>) KH550-B4/PUE.</p>
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<p>Stress–strain curves of PUE matrix and different composites with (<b>a</b>) KH560-B3/PUE and (<b>b</b>) KH560-B4/PUE.</p>
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<p>Loss modulus, storage modulus, and loss factor curve of KH550 BMF/PUE composites: (<b>a</b>) loss modulus, (<b>b</b>) storage modulus, and (<b>c</b>,<b>d</b>) loss factor of different KH550 BMF/PUE composites.</p>
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<p>Loss modulus, storage modulus, and loss factor curve of KH560 BMF/PUE composites: (<b>a</b>) loss modulus, (<b>b</b>) storage modulus, and (<b>c</b>,<b>d</b>) loss factor of different KH560 BMF/PUE composites.</p>
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<p>Transmission loss curves from 0 to 1600 Hz for different modified BMF/PUE composites: (<b>a</b>) 1% KH550 with different ball milling time, (<b>b</b>) same milling time with different KH550 content, (<b>c</b>) 1% KH560 with different ball milling time, and (<b>d</b>) same milling time with different KH560 content.</p>
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<p>Cross-sectional SEM images of 1 wt%-KH550-B4/PUE.</p>
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<p>Cross-sectional SEM images of 1.5 wt%-KH560-B4/PUE.</p>
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<p>SEM images of KH550 (<b>left</b>) and KH560 (<b>right</b>) surface-modified basalt fibers.</p>
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12 pages, 2100 KiB  
Article
Evaluation of Length and Fiber Count Determinations for Natural and Synthetic Microfibers Using the OpTest Fiber Quality Analyzer
by Michael Santiago Cintron, Chanel A. Fortier and Sunghyun Nam
Microplastics 2024, 3(4), 730-741; https://doi.org/10.3390/microplastics3040045 - 6 Dec 2024
Viewed by 636
Abstract
Microfibers are small fiber particles that range from 1 µm to 5 mm in length, generated through the home laundering and daily wear of textile garments. Microfibers stemming from synthetic textiles are a global pollution problem marked by their slow biodegradation and steady [...] Read more.
Microfibers are small fiber particles that range from 1 µm to 5 mm in length, generated through the home laundering and daily wear of textile garments. Microfibers stemming from synthetic textiles are a global pollution problem marked by their slow biodegradation and steady environmental accumulation. Thus, the quantification and study of factors controlling their generation is of interest. The aim of the current study included exploring the use of a Fiber Quality Analyzer-360 (FQA) for examining fiber counts and lengths of microfibers derived from cotton, flax, ramie, hemp, acrylic, polyester, viscose, and polyamide, and to explore if additional preparation steps, such as sonication, would improve microfiber detection by the system. While probe sonication led to higher fiber counts for most microfiber types, average microfiber lengths were statistically similar for most samples, with only the hemp and ramie samples showing statistically shorter microfibers following sonication. FQA detection estimates for cotton, viscose, and ramie microfibers were high, at 99, 101, and 116% for viscose, flax, and cotton, respectively. In contrast, synthetic microfibers of acrylic, polyamide and polyester showed 77, 43, and 14% detection rates, respectively. The high detection rate for the cotton sample is partly due to the higher fineness value obtained from the gravimetric determination. A similar calculation using AFIS fineness showed 86% detection. These observations confirm the significance of properly suspending the samples to accurately quantify microfibers while using the FQA system. Furthermore, the reduced detection of the examined synthetic microfibers suggests the limitations of the FQA as a technique for the direct comparison of natural and synthetic microfiber counts. Full article
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<p>Optical microscopy images of cellulose-based (<b>a</b>–<b>e</b>) and synthetic (<b>f</b>–<b>h</b>) microfibers at 1000× magnification: (<b>a</b>) cotton, (<b>b</b>) flax, (<b>c</b>) hemp, (<b>d</b>) ramie, (<b>e</b>) viscose, (<b>f</b>) acrylic, (<b>g</b>) polyester, and (<b>h</b>) polyamide.</p>
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<p>Relative distribution of microfiber length (L<sub>n</sub>) values for eight microfiber samples as detected with the FQA instrument: cotton (<b>top left</b>), flax (<b>top right</b>), hemp (<b>top middle left</b>), ramie (<b>top middle right</b>), viscose (<b>bottom middle left</b>), acrylic (<b>bottom middle right</b>), polyester (<b>bottom left</b>), and polyamide (<b>bottom right</b>). Each relative distribution displays the length (L<sub>n</sub>) measurements observed for 10 microfiber samples (2 mg) that were sonicated prior to examination (light red histograms) or without sonication (light blue histogram). The darker blue histogram columns represent areas of overlap.</p>
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<p>ESEM images of cellulose-based microfibers at 1000× magnification: (<b>a</b>) cotton, (<b>b</b>) flax, (<b>c</b>) hemp, (<b>d</b>) ramie, and (<b>e</b>) viscose.</p>
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<p>Bivariate plots of fiber counts values versus fineness (AFIS) and L<sub>n</sub> versus fiber count. The bivariate plot of fiber counts versus fineness (<b>left</b>) includes values for six cotton standards from a previous study [<a href="#B1-microplastics-03-00045" class="html-bibr">1</a>], and those of cotton, polyester, and polyamide from the current study. The size of each sample is proportional to its L<sub>n</sub> value. The bivariate plot of L<sub>n</sub> and fiber counts (<b>right</b>) includes the same microfiber samples. The plot size of each sample is proportional to its fineness value. A linear fit of the cotton standards (black trace) is displayed in each trace.</p>
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18 pages, 31550 KiB  
Article
Construction of Silk Fibroin 3D Microfiber Scaffolds and Their Applications in Anti-Osteoporosis Drug Prediction
by Hua Xu, Mengfan Huang, Mengyuan Zhou, Rong Guo, Kunming Qin and Zibo Dong
Molecules 2024, 29(23), 5681; https://doi.org/10.3390/molecules29235681 - 30 Nov 2024
Viewed by 639
Abstract
Silk microfiber scaffolds have garnered increasing interest due to their outstanding properties, with degumming being the process used to extract the sericin from the cocoon. In the present study, an attempt to tune the biodegradation period of silk through degumming with various sodium [...] Read more.
Silk microfiber scaffolds have garnered increasing interest due to their outstanding properties, with degumming being the process used to extract the sericin from the cocoon. In the present study, an attempt to tune the biodegradation period of silk through degumming with various sodium borohydride (NaBH4) concentrations and degumming times was studied. We considered the process, the number of baths used, and the salt concentration. Herein, we report a novel method of expanding microfibers from two-dimensional (2D) to three-dimensional (3D) using a modified gas-foaming technique. Porous three-dimensional (3D) silk fibroin (SF) scaffolds were fabricated by the SF fibers, which were extracted by the NaBH4 degumming method and NaBH4 gas-foaming approach. This study showed that higher salt concentrations, reaching 1.5% in a double bath, effectively removed sericin from silk fibroin, resulting in clean, smooth 3D scaffolds. These scaffolds were then fabricated using a freeze-drying method. The scaffolds were then submerged in solutions containing semen cuscutae (SC) and their surfaces were coated with various percentages of total flavonoids. The scaffolds had no toxicity to the cells in vitro. This work provides a new route for achieving a TFSC-loaded scaffold; it is proved that the coated silk fibroin fiber scaffold has excellent compatibility. Compared with non-drug-loaded silk scaffolds, drug-loaded silk scaffolds promote cell growth. Full article
(This article belongs to the Section Materials Chemistry)
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<p>The chemical structure of silk fibroin and silk sericin.</p>
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<p>(<b>A</b>) The degumming ratio of silkworm cocoons treated with varying concentrations and varying baths; (<b>B</b>) FTIR spectra of silkworm cocoons and degummed silk fibers (1% NaBH<sub>4</sub>, 12 h); (<b>C</b>) SEM micrographs of the fibers from the 12 degumming treatments, (<b>a1</b>–<b>a4</b>) single bath, (<b>b1</b>–<b>b4</b>) double bath and (<b>c1</b>–<b>c4</b>) triple bath.</p>
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<p>Preparation of SF 3D microfiber scaffolds. (<b>A</b>) Schematic illustration of the fabrication of expanded SF microfiber scaffolds. (<b>B</b>) Photographs showing the silk scaffolds before and after treatment with 1% NaBH<sub>4</sub>. (<b>a</b>) Without Soaking; (<b>b</b>) Soaking in NaBH<sub>4</sub> solutions for 2 h; (<b>c</b>) Soaking in NaBH<sub>4</sub> solutions for 3 h; (<b>d</b>) Soaking in NaBH<sub>4</sub> solutions for 4 h. (<b>C</b>) Morphology of silk microfiber scaffold SEM images before and after treatment with 1% NaBH<sub>4</sub>. (<b>a</b>) Without Soaking; (<b>b</b>) Soaking in NaBH<sub>4</sub> solutions for 2 h; (<b>c</b>) Soaking in NaBH<sub>4</sub> solutions for 3 h; (<b>d</b>) Soaking in NaBH<sub>4</sub> solutions for 4 h.</p>
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<p>In vitro degradation behavior of degummed silk scaffold. (<b>A</b>) SEM images of degummed silk after enzymatic degradation with time; (<b>a1</b>–<b>a4</b>) 0.5% NaBH<sub>4</sub>, (<b>b1</b>–<b>b4</b>) 1% NaBH<sub>4</sub>, (<b>c1</b>–<b>c4</b>) 1.5%NaBH<sub>4</sub>, (<b>d1</b>–<b>d4</b>) 2% NaBH<sub>4</sub>. (<b>B</b>) 0.5% NaBH<sub>4</sub>, 12 h, (<b>C</b>) 1% NaBH<sub>4</sub>, 12 h, (<b>D</b>) 1.5% NaBH<sub>4</sub>, 12 h, (<b>E</b>) 2% NaBH<sub>4</sub>, 12 h, FTIR spectra of degummed silk scaffolds after enzymatic degradation with time. (<b>F</b>) Plausible mechanism for the degradation of SF scaffolds.</p>
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<p>In vivo degradation behavior of the degummed silk scaffold. (<b>A</b>) Schematic illustration of subcutaneous implantation of the expanded 3D silk microfiber scaffold; (<b>B</b>) Histological image of H&amp;E staining of the subcutaneously implanted silk fiber scaffold at 1 week, 2 weeks, 3 weeks, and 4 weeks. Green square indicate enlarging some areas of the implanted silk scaffold.</p>
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<p>TFSC structure.</p>
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<p>The HPLC fingerprints of the mixed standard substance (<b>A</b>) and TFSC samples (<b>B</b>).</p>
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<p>Schematic illustration of the fabrication and characterization of SF 3D microfiber-coated scaffolds. (<b>A</b>) Schematic diagram of the fabrication of 3D microfiber-coated scaffolds; (<b>B</b>) The cross-sectional view of SF 3D microfiber-coated scaffolds; (<b>C</b>) SEM images of 3D microfiber-coated scaffolds: (<b>a</b>) NO group: scaffold samples without coating; (<b>b</b>) TFSC-SF-1 group: The degummed microfibers scaffolds were soaked in 1 mg/mL TFSC solution and then dipped in a solution containing 4 mg/mL TFSC, 7% SF at a volume ratio of 1:10; (<b>c</b>) TFSC-SF-2 group: The degummed microfibers scaffolds were soaked in 4 mg/mL TFSC solution and then dipped in a solution containing 4 mg/mL TFSC, 7% SF at a volume ratio of 1:10; (<b>d</b>) TFSC-SF-3 group: The degummed microfibers scaffolds were soaked in 7 mg/mL TFSC solution and then dipped in a solution containing 4 mg/mL TFSC, 7% SF at a volume ratio of 1:10; (<b>D</b>) FTIR spectra of DG silk-coated scaffolds, DG silk scaffolds and cocoon; (<b>E</b>) XRD spectrum of DG silk-coated scaffolds, DG silk scaffolds and cocoon; (<b>F</b>) Thermogravimetric (TG) curves of DG silk-coated scaffolds, DG silk scaffolds and cocoon; (<b>G</b>) Derivative thermogravimetric (DTG) curves of DG silk-coated scaffolds, DG silk scaffolds and cocoon.</p>
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<p>Cell viability investigation. (<b>A</b>) CCK-8 assay result of MC 3T3-E1 cell proliferation after 1, 3, and 5 days, * indicate significance; (<b>B</b>) Morphology of MC 3T3-E1 cells under the effect of the control, SF, and SF/TFSC.</p>
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<p>Cell viability investigation. (<b>A</b>) CCK-8 assay result of MC 3T3-E1 cell proliferation after 1, 3, and 5 days, * indicate significance; (<b>B</b>) Morphology of MC 3T3-E1 cells under the effect of the control, SF, and SF/TFSC.</p>
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<p>The procedure followed for silk fibroin degumming is outlined in the accompanying scheme.</p>
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<p>The schematic representation illustrates the mechanism by which TFSC inhibits TRAF6 and NOX1-induced osteoclastogenesis and a schematic illustration of SF 3D microfiber-coated scaffolds for bone regeneration.</p>
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23 pages, 19499 KiB  
Article
Investigation of 3D Printed Self-Sensing UHPC Composites Using Graphite and Hybrid Carbon Microfibers
by Han Liu, Simon Laflamme, Bin Cai, Ping Lyu, Sri Sritharan and Kejin Wang
Sensors 2024, 24(23), 7638; https://doi.org/10.3390/s24237638 - 29 Nov 2024
Viewed by 631
Abstract
This paper explores the development of 3D-printed self-sensing Ultra-High Performance Concrete (UHPC) by incorporating graphite (G) powder, milled carbon microfiber (MCMF), and chopped carbon microfiber (CCMF) as additives into the UHPC matrix to enhance piezoresistive properties while maintaining workability for 3D printing. Percolation [...] Read more.
This paper explores the development of 3D-printed self-sensing Ultra-High Performance Concrete (UHPC) by incorporating graphite (G) powder, milled carbon microfiber (MCMF), and chopped carbon microfiber (CCMF) as additives into the UHPC matrix to enhance piezoresistive properties while maintaining workability for 3D printing. Percolation curves were established to identify optimal filler inclusion levels, and a series of compressive tests, including quasi-static cyclic, dynamic cyclic, and monotonic compressive loading, were conducted to evaluate the piezoresistive and mechanical performance of 29 different mix designs. It was found that incorporating G powder improved the conductivity of the UHPC but decreased compressive strength for both mold-cast and 3D-printed specimens. However, incorporating either MCMF or CCMF into the UHPC resulted in the maximum 9.8% and 19.2% increase in compressive strength and Young’s modulus, respectively, compared to the plain UHPC. The hybrid combination of MCMF and CCMF showed particularly effective in enhancing sensing performance, achieving strain linearity over 600 με. The best-preforming specimens (3G250M250CCMF) were fabricated using 3 wt% of G, 0.25 wt% of MCMF, and 0.25 wt% of CCMF, yielding a maximum strain gauge factor of 540, a resolution of 68 με, and an accuracy of 4.5 με under axial compression. The 3D-printed version of the best-performing specimens exhibited slightly diminished piezoresistive and mechanical behaviors compared to their mold-cast counterparts, yielding a maximum strain gauge factor of 410, a resolution of 99 με, and an accuracy of 8.6 με. Full article
(This article belongs to the Section Sensor Materials)
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<p>Illustration of the electrical percolation process: (<b>a</b>) UHPC-only (without fiber); (<b>b</b>) G-only; (<b>c</b>) G + MCMF; (<b>d</b>) G + CCMF; (<b>e</b>) G + MCMF + CCMF.</p>
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<p>Magnified pictures of dry mixture components.</p>
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<p>Fabrication process of the mold-cast and 3D-printed self-sensing UHPC specimen.</p>
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<p>(<b>a</b>) Picture of the 3D printer; (<b>b</b>) schematic illustration of the 3D-printed rectangular prism showing the overall geometry dimension and the directional description of 3DP process; (<b>c</b>) directional description of the nozzle path; (<b>d</b>) picture of the 3DP process.</p>
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<p>Pictures showing (<b>a</b>) overall experimental setup used to characterize sensing properties; (<b>b</b>) closeup view on a tested specimen; (<b>c</b>) 3DP specimen after brittle failure.</p>
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<p>Percolation curves obtained from 28-day resistivity measurements for (<b>a</b>) single MCMF versus CCMF doping with the inset showing the percolation curve for G filling; (<b>b</b>) dual doping (MCMF + CCMF).</p>
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<p>Strain sensing performance for key mix designs under quasi-static cyclic loading test for specimens (<b>a</b>) 0G0CMF; (<b>b</b>) 3G0CMF; (<b>c</b>) 3G1000MCMF; (<b>d</b>) 3D500CCMF; (<b>e</b>) 3G125M500CCMF; (<b>f</b>) 3G250M250CCMF; (<b>g</b>) 3G250M500CCMF; (<b>h</b>) 3DP-3G250M250CCMF. I don’t think we used hyphen in this figure. All symbols are minus sign. Same as below.</p>
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<p>Time histories of electrical and strain measurements under increased loading frequency for specimens (<b>a</b>) 0G0CMF; (<b>b</b>) 3G0CMF; (<b>c</b>) 3G1000MCMF; (<b>d</b>) 3D500CCMF; (<b>e</b>) 3G125M500CCMF; (<b>f</b>) 3G250M250CCMF; (<b>g</b>) 3G250M500CCMF; (<b>h</b>) 3DP-3G250M250CCMF.</p>
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<p>Stress strain curve for (<b>a</b>) G dopant; (<b>b</b>) selected 3DP versus mold-cast specimens.</p>
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<p>Plots of -FCR measured from the monotonic compressive loading test for specimens under representative mix designs.</p>
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