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Keywords = fluoroalkyl silane

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7 pages, 974 KB  
Communication
Synthesis and Structures of Trifluoromethylborates [pinB(Aryl)CF3]: pinB = 4,4,5,5-Tetramethyl-1,3,2-dioxaborolane
by Yu-En Huang and Shigekazu Ito
Molbank 2026, 2026(3), M2183; https://doi.org/10.3390/M2183 - 2 Jun 2026
Viewed by 177
Abstract
Fluoroalkyl-substituted organoboron compounds are valuable building blocks for organic synthesis and for the development of functional molecules in medicinal chemistry, agrochemicals, and materials science. Building on our previous work on difluoromethyl-substituted borates, we report the synthesis and structural characterization of trifluoromethylated borates, 2-aryl-4,4,5,5-tetramethyl-2-(trifluoromethyl)-1,3,2-dioxaborolan-2-uide [...] Read more.
Fluoroalkyl-substituted organoboron compounds are valuable building blocks for organic synthesis and for the development of functional molecules in medicinal chemistry, agrochemicals, and materials science. Building on our previous work on difluoromethyl-substituted borates, we report the synthesis and structural characterization of trifluoromethylated borates, 2-aryl-4,4,5,5-tetramethyl-2-(trifluoromethyl)-1,3,2-dioxaborolan-2-uide salts ([pinB(Aryl)CF3]). Treatment of pinB–Aryl boronates (pinB = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane) with trimethyl(trifluoromethyl)silane (Ruppert–Prakash reagent) in the presence of potassium tert-butoxide and 18-crown-6 ether (18-C-6) afforded the corresponding trifluoromethylated borates as isolable crystalline compounds. Compared with the related difluoromethylated borates, the CF3 substituent increases the tendency of [pinB(Aryl)CF3] to exhibit hygroscopic behavior, as supported by a hydrated crystal structure and the formation of a hygroscopic product. The isolable trifluoromethylborates can serve as reservoirs of electrophilic trifluoromethyl radicals upon oxidation. Full article
(This article belongs to the Section Structure Determination)
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30 pages, 3841 KB  
Article
Eco-Friendly Octylsilane-Modified Amino-Functional Silicone Coatings for a Durable Hybrid Organic–Inorganic Water-Repellent Textile Finish
by Mariam Hadhri, Claudio Colleoni, Agnese D’Agostino, Mohamed Erhaim, Raphael Palucci Rosa, Giuseppe Rosace and Valentina Trovato
Polymers 2025, 17(11), 1578; https://doi.org/10.3390/polym17111578 - 5 Jun 2025
Cited by 7 | Viewed by 4689
Abstract
The widespread phase-out of long-chain per- and poly-fluoroalkyl substances (PFASs) has created an urgent need for durable, fluorine-free water-repellent finishes that match the performance of legacy chemistries while minimising environmental impact. Here, the performance of an eco-friendly hybrid organic–inorganic treatment obtained by the [...] Read more.
The widespread phase-out of long-chain per- and poly-fluoroalkyl substances (PFASs) has created an urgent need for durable, fluorine-free water-repellent finishes that match the performance of legacy chemistries while minimising environmental impact. Here, the performance of an eco-friendly hybrid organic–inorganic treatment obtained by the in situ hydrolysis–condensation of triethoxy(octyl)silane (OS) in an amino-terminated polydimethylsiloxane (APT-PDMS) aqueous dispersion was investigated. The sol was applied to plain-weave cotton and polyester by a pad-dry-cure process and benchmarked against a commercial fluorinated finish. Morphology and chemistry were characterised by SEM–EDS, ATR-FTIR, and Raman spectroscopy; wettability was assessed by static contact angle, ISO 4920 spray ratings, and AATCC 193 water/alcohol repellence; and durability, handle, and breathability were evaluated through repeated laundering, bending stiffness, and water-vapour transmission rate measurements. The silica/PDMS coating formed a uniform, strongly adherent nanostructured layer conferring static contact angles of 130° on cotton and 145° on polyester. After five ISO 105-C10 wash cycles, the treated fabrics still displayed a spray rating of 5/5 and AATCC 193 grade 7, outperforming or equalling the fluorinated control, while causing ≤5% loss of water-vapour permeability and only a marginal increase in bending stiffness. These results demonstrate that the proposed one-step, water-borne sol–gel process affords a sustainable, industrially scalable route to high-performance, durable, water-repellent finishes for both natural and synthetic textiles, offering a viable alternative to PFAS-based chemistry for outdoor apparel and technical applications. Full article
(This article belongs to the Special Issue Environmentally Friendly Textiles, Fibers and Their Composites)
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12 pages, 3482 KB  
Article
Chemical Instability-Induced Wettability Patterns on Superhydrophobic Surfaces
by Tianchen Chen and Faze Chen
Micromachines 2024, 15(3), 329; https://doi.org/10.3390/mi15030329 - 27 Feb 2024
Cited by 8 | Viewed by 2190
Abstract
Chemical instability of liquid-repellent surfaces is one of the nontrivial hurdles that hinders their real-world applications. Although much effort has been made to prepare chemically durable liquid-repellent surfaces, little attention has been paid to exploit the instability for versatile use. Herein, we propose [...] Read more.
Chemical instability of liquid-repellent surfaces is one of the nontrivial hurdles that hinders their real-world applications. Although much effort has been made to prepare chemically durable liquid-repellent surfaces, little attention has been paid to exploit the instability for versatile use. Herein, we propose to create hydrophilic patterns on a superhydrophobic surface by taking advantage of its chemical instability induced by acid solution treatment. A superhydrophobic Cu(OH)2 nanoneedle-covered Cu plate that shows poor stability towards HCl solution (1.0 M) is taken as an example. The results show that 2.5 min of HCl solution exposure leads to the etching of Cu(OH)2 nanoneedles and the partial removal of the self-assembled fluoroalkyl silane molecular layer, resulting in the wettability transition from superhydrophobocity to hydrophilicity, and the water contact angle decreases from ~160° to ~30°. Hydrophilic dimples with different diameters are then created on the superhydrophobic surfaces by depositing HCl droplets with different volumes. Afterwards, the hydrophilic dimple-patterned superhydrophobic surfaces are used for water droplet manipulations, including controlled transfer, merging, and nanoliter droplet deposition. The results thereby verify the feasibility of creating wettability patterns on superhydrophobic surfaces by using their chemical instability towards corrosive solutions, which broadens the fabrication methods and applications of functional liquid-repellent surfaces. Full article
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14 pages, 5382 KB  
Article
Development of a Carbon Nanotube-Enhanced FAS Bilayer Amphiphobic Coating for Biological Fluids
by Sumona Paul, Lingfen Rao, Louis H. Stein, Arash Salemi and Somenath Mitra
Nanomaterials 2023, 13(24), 3138; https://doi.org/10.3390/nano13243138 - 14 Dec 2023
Cited by 4 | Viewed by 2426
Abstract
This study reports the development of a novel amphiphobic coating. The coating is a bilayer arrangement, where carbon nanotubes (CNTs) form the underlayer and fluorinated alkyl-silane (FAS) forms the overlayer, resulting in the development of highly amphiphobic coatings suitable for a wide range [...] Read more.
This study reports the development of a novel amphiphobic coating. The coating is a bilayer arrangement, where carbon nanotubes (CNTs) form the underlayer and fluorinated alkyl-silane (FAS) forms the overlayer, resulting in the development of highly amphiphobic coatings suitable for a wide range of substrates. The effectiveness of these coatings is demonstrated through enhanced contact angles for water and artificial blood plasma fluid on glass, stainless steel, and porous PTFE. The coatings were characterized using Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), atomic force microscopy (AFM), and contact angle (CA) measurements. The water contact angles achieved with the bilayer coating were 106 ± 2°, 116 ± 2°, and 141 ± 2° for glass, stainless steel, and PTFE, respectively, confirming the hydrophobic nature of the coating. Additionally, the coating displayed high repellency for blood plasma, exhibiting contact angles of 102 ± 2°, 112 ± 2°, and 134 ± 2° on coated glass, stainless steel, and PTFE surfaces, respectively. The presence of the CNT underlayer improved plasma contact angles by 29%, 21.7%, and 16.5% for the respective surfaces. The presence of the CNT layer improved surface roughness significantly, and the average roughness of the bilayer coating on glass, stainless steel, and PTFE was measured to be 488 nm, 301 nm, and 274 nm, respectively. Mechanistically, the CNT underlayer contributed to the surface roughness, while the FAS layer provided high amphiphobicity. The maximum effect was observed on modified glass, followed by stainless steel and PTFE surfaces. These findings highlight the promising potential of this coating method across diverse applications, particularly in the biomedical industry, where it can help mitigate complications associated with device–fluid interactions. Full article
(This article belongs to the Section 2D and Carbon Nanomaterials)
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15 pages, 4620 KB  
Article
Influence of Perfluorooctanoic Acid on Structural, Morphological, and Optical Properties of Hybrid Silica Coatings on Glass Substrates
by Violeta Purcar, Valentin Rădiţoiu, Florentina Monica Raduly, Alina Rădiţoiu, Simona Căprărescu, Adriana Nicoleta Frone, Raluca Şomoghi, Mihai Anastasescu, Hermine Stroescu and Cristian-Andi Nicolae
Appl. Sci. 2023, 13(3), 1669; https://doi.org/10.3390/app13031669 - 28 Jan 2023
Cited by 6 | Viewed by 2726
Abstract
In recent years, various coatings based on fluorinated materials, used in a commercial application, have been created through many preparation routes. However, the techniques utilized to realize these coatings required either expensive and complex equipment, imply multiple manufacturing steps, or are time- or [...] Read more.
In recent years, various coatings based on fluorinated materials, used in a commercial application, have been created through many preparation routes. However, the techniques utilized to realize these coatings required either expensive and complex equipment, imply multiple manufacturing steps, or are time- or cost-consuming. In this paper, the major target was to develop fluorinated hybrid coatings presenting sustainable hydrophobicity and good transparency simultaneously. The sol–gel method was proposed to obtain these fluorinated hybrid coatings because it does not require expensive equipment, or the existence of stabilizing agents that reduce the storage period, it consumes less energy, and it is easy to implement. The influence of perfluorooctanoic acid, utilized in the sol–gel processing of hybrid silica materials, on the structural, morphological, and optical properties of coatings deposited on glass substrates, was evaluated. Different silane precursors (tetraethyl orthosilicate (TEOS), triethoxymethylsilane (MTES), and trimethoxyhexadecylsilane (HDTMES)) were utilized to synthesize hybrid silica materials. The properties of the obtained materials were characterized by FTIR, UV–Vis, TEM, TGA, AFM, Ellipsometry, and Contact Angle analyses. FTIR spectroscopy shows the formation of a silica network tailored with organofunctional and fluoroalkyl groups. The fluorinated silica coatings presented smooth surfaces and good transparency, with a transmittance of ~90% in the visible range. It was found that the fluorinated silica materials improved the coating’s hydrophobicity (~110° in contact angle with water). These fluorinated silica materials can create multifunctional structures with antireflective and hydrophobic coatings for possible optical devices. Full article
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6 pages, 1212 KB  
Article
Influencing the Crystalline Domains of Poly(vinylidenedifluoride) Composites Using Fluorinated Silica Nanoparticles as Drop-In Modifiers
by Nathan J. Weeks, Cole R. Phelps, Enrique T. Gazmin and Scott T. Iacono
Molecules 2022, 27(23), 8398; https://doi.org/10.3390/molecules27238398 - 1 Dec 2022
Viewed by 2172
Abstract
Improvements to fluoropolymer processing techniques by way of utilizing nanoparticles as drop-in processing aids have pronounced effects on bulk composite properties. In this work, we prepared fluoroalkyl-silanized silica nanoparticles (F-SiNPs, ca. 200 nm) that were solvent-blended with polyvinylenedifluoride (PVDF) in order to prepare [...] Read more.
Improvements to fluoropolymer processing techniques by way of utilizing nanoparticles as drop-in processing aids have pronounced effects on bulk composite properties. In this work, we prepared fluoroalkyl-silanized silica nanoparticles (F-SiNPs, ca. 200 nm) that were solvent-blended with polyvinylenedifluoride (PVDF) in order to prepare composites with varying weight fractions. We demonstrated that the ability to functionalize SiNPs with long fluoroalkylchains that induced co-crystallization with the PVDF matrix, resulting in uniform particle dispersion and improved interlaminate adhesion. This was quantitatively investigated using calorimetry and thermogravimetric analysis, which showed a decrease in the bulk crystallinity of the virgin PVDF from 37% to 10% with minimal 10 wt % F-SiNP loading, rendering a nearly amorphous PVDF. Additional discussions in this work include the effects of various bare and fluoroalkyl-functionalized SiNP loadings on the amorphous and crystalline domains of the PVDF matrix, as well as thermal decomposition. Full article
(This article belongs to the Special Issue Advances in Fluoropolymers)
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17 pages, 4470 KB  
Article
Facile Synthesis of Fluorinated Polysilazanes and Their Durable Icephobicity on Rough Al Surfaces
by Tien N. H. Lo, Sung Woo Hong, Ha Soo Hwang and In Park
Polymers 2022, 14(2), 330; https://doi.org/10.3390/polym14020330 - 14 Jan 2022
Cited by 13 | Viewed by 4031
Abstract
Superhydrophobic Al surfaces with excellent durability and anti-icing properties were fabricated by coating dual-scale rough Al substrates with fluorinated polysilazane (FPSZ). Flat Al plates were etched using an acidic solution, followed by immersion in boiling water to generate hierarchical micro-nano structures on their [...] Read more.
Superhydrophobic Al surfaces with excellent durability and anti-icing properties were fabricated by coating dual-scale rough Al substrates with fluorinated polysilazane (FPSZ). Flat Al plates were etched using an acidic solution, followed by immersion in boiling water to generate hierarchical micro-nano structures on their surfaces. The FPSZ coatings were synthesized by grafting 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (FAS-17), a fluoroalkyl silane), onto methylpolysilazane, an organopolysilazane (OPSZ) backbone. The high water contact angle (175°) and low sliding angle (1.6°) of the FPSZ-coated sample with an FAS-17 content of 17.3 wt% promoted the efficient removal of a frozen ice column with a low ice adhesion strength of 78 kPa at −20.0 °C (70% relative humidity), which was 4.3 times smaller than that of an OPSZ-coated surface. The FPSZ-coated Al surface suppressed ice nucleation, leading to a decrease in ice nucleation temperature from −19.5 to −21.9 °C and a delay in freezing time from 334 to 4914 s at −19.0 °C compared with the OPSZ-coated Al surface. Moreover, after 40 icing–melting cycles the freezing temperature of a water droplet on the FPSZ-coated Al surface remained unchanged, whereas that on the FAS-17-coated Al surface increased from −22.3 to −20.7 °C. Therefore, the durability of the polymeric FPSZ coating was superior to that of the FAS-17 monolayer coating. Full article
(This article belongs to the Special Issue Functional Polymer Coatings II)
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8 pages, 2773 KB  
Proceeding Paper
The Influence of Adding a Functionalized Fluoroalkyl Silanes (PFDTES) into a Novel Silica-Based Hybrid Coating on Corrosion Protection Performance on an Aluminium 2024-t3 Alloy
by Magdi H. Mussa, Yaqub Rahaq, Sarra Takita, Farah D. Zahoor, Nicholas Farmilo and Oliver Lewis
Mater. Proc. 2021, 7(1), 6; https://doi.org/10.3390/IOCPS2021-11240 - 30 Oct 2021
Cited by 4 | Viewed by 2882
Abstract
Silica-based coatings prepared using sol-gel polymerizing technology have been shown to exhibit excellent chemical stability combined with reducing the corrosion of metal substrates, showing promising use in aerospace and marine applications to protect light alloys. Moreover, this technology is an eco-friendly technique route [...] Read more.
Silica-based coatings prepared using sol-gel polymerizing technology have been shown to exhibit excellent chemical stability combined with reducing the corrosion of metal substrates, showing promising use in aerospace and marine applications to protect light alloys. Moreover, this technology is an eco-friendly technique route for producing surface coatings, showing high potential for replacing toxic pre-treatment coatings of traditional conversation chromate coatings. This study aims to investigate the enhancement in corrosion protection of a hybrid-organic-inorganic silica-based coating cured at 80 °C by increasing the hydrophobicity to work on the aluminium 2024-T3 alloy. This approach involving a novel silica-based hybrid coating was prepared by introducing 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) into the base hybrid formula created from tetraethylorthosilicatesilane (TEOS) and triethoxymethylsilane (MTMS) precursors; this formula was enhanced by introducing a Polydimethylsiloxane polymer (PDMS). The corrosion protection properties of these coatings were examined by being immersed in 3.5% NaCl with electrochemical impedance testing (EIS) and Potentiodynamic polarization scanning (PDPS). The chemical elements confirmation was performed using infrared spectroscopy (ATR-FTIR); all this was supported by analysing the surface morphology before and after the immersion by using scanning electron microscopy (SEM). The results of the electrochemical impedance testing analyses reveal the new open finite-length diffusion circuit element due to electrolyte media diffusion prevented by fluorinated groups. Additionally, it shows increases in corrosion protection arising from the increasing hydrophobicity of the fluorinated coating compared to other formulas cured under similar conditions and bare substrate. Additionally, the modified sol-gel exhibited improved resistance to cracking, while the increased hydrophobicity may also promote self-cleaning. Full article
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14 pages, 21768 KB  
Article
Fabrication and Characterization of Hydrophobic Porous Metallic Membranes for High Temperature Applications
by Sara Claramunt, Muhammad Khurram, Walther Benzinger, Manfred Kraut and Roland Dittmeyer
Processes 2021, 9(5), 809; https://doi.org/10.3390/pr9050809 - 5 May 2021
Cited by 7 | Viewed by 6296
Abstract
Hydrophobic porous metallic membranes can be integrated in a microreactor for in situ separation of steam at high temperatures. This study investigates the fabrication and characterization of hydrophobic coatings on metallic substrates. Two different coating methods were explored: (1) Plasma Enhanced—Chemical Vapor Deposition [...] Read more.
Hydrophobic porous metallic membranes can be integrated in a microreactor for in situ separation of steam at high temperatures. This study investigates the fabrication and characterization of hydrophobic coatings on metallic substrates. Two different coating methods were explored: (1) Plasma Enhanced—Chemical Vapor Deposition (PE-CVD) to form amorphous carbon silicon-doped a-C:H:Si:O thin films and (2) Direct Immersion in fluoroalkyl silane (FAS-13) solution using dip coating to form Self-Assembled Monolayers. The results on wettability as well as SEM images and EDS/WDS analyses indicate that the coated sintered stainless steel membranes are adequate as hydrophobic surfaces, maintaining the porosity of the substrate and withstanding high temperatures. Especially the FAS-13 coating shows very good resistance to temperatures higher than 250 °C. These findings are of special significance for the fabrication of porous metal membranes for separation of steam in high temperature applications. Full article
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11 pages, 3941 KB  
Article
Hydrophobic/Oleophilic Structures Based on MacroPorous Silicon: Effect of Topography and Fluoroalkyl Silane Functionalization on Wettability
by Pilar Formentín and Lluís F. Marsal
Nanomaterials 2021, 11(3), 670; https://doi.org/10.3390/nano11030670 - 9 Mar 2021
Cited by 12 | Viewed by 4285
Abstract
The effect of the morphology and chemical composition of a surface on the wettability of porous silicon structures is analyzed in the present work. Hydrophobic and superhydrophobic macroporous substrates are attractive for different potential applications. Herein, different hydrophobic macroporous silicon structures were fabricated [...] Read more.
The effect of the morphology and chemical composition of a surface on the wettability of porous silicon structures is analyzed in the present work. Hydrophobic and superhydrophobic macroporous substrates are attractive for different potential applications. Herein, different hydrophobic macroporous silicon structures were fabricated by the chemical etching of p-type silicon wafers in a solution based on hydrofluoric acid and coated with a fluoro silane self-assembled monolayer. The surface morphology of the final substrate was characterized using a scanning electron microscope. The wettability was assessed from contact angle measurements using water and organic solvents that present low surface energy. The experimental data were compared with the classical wetting states theoretical models described in the literature. Perfluoro-silane functionalized macroporous silicon surfaces presented systematically higher contact angles than untreated silicon substrates. The influence of porosity on the surface wettability of macoporous silicon structures has been established. These results suggest that the combination of etching conditions with a surface chemistry modification could lead to hydrophobic/oleophilic or superhydrophobic/oleophobic structures. Full article
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14 pages, 3999 KB  
Article
Rapid Fabrication of Epidermal Paper-Based Electronic Devices Using Razor Printing
by Behnam Sadri, Debkalpa Goswami and Ramses V. Martinez
Micromachines 2018, 9(9), 420; https://doi.org/10.3390/mi9090420 - 22 Aug 2018
Cited by 24 | Viewed by 8294
Abstract
This work describes the use of a benchtop razor printer to fabricate epidermal paper-based electronic devices (EPEDs). This fabrication technique is simple, low-cost, and compatible with scalable manufacturing processes. EPEDs are fabricated using paper substrates rendered omniphobic by their cost-effective silanization with fluoroalkyl [...] Read more.
This work describes the use of a benchtop razor printer to fabricate epidermal paper-based electronic devices (EPEDs). This fabrication technique is simple, low-cost, and compatible with scalable manufacturing processes. EPEDs are fabricated using paper substrates rendered omniphobic by their cost-effective silanization with fluoroalkyl trichlorosilanes, making them inexpensive, water-resistant, and mechanically compliant with human skin. The highly conductive inks or thin films attached to one of the sides of the omniphobic paper makes EPEDs compatible with wearable applications involving wireless power transfer. The omniphobic cellulose fibers of the EPED provide a moisture-independent mechanical reinforcement to the conductive layer. EPEDs accurately monitor physiological signals such as ECG (electrocardiogram), EMG (electromyogram), and EOG (electro-oculogram) even in high moisture environments. Additionally, EPEDs can be used for the fast mapping of temperature over the skin and to apply localized thermotherapy. Our results demonstrate the merits of EPEDs as a low-cost platform for personalized medicine applications. Full article
(This article belongs to the Special Issue Flexible Electronics: Fabrication and Ubiquitous Integration)
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