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Keywords = organosilane films

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18 pages, 4348 KiB  
Article
The Combined Effects of Additives on the Conventional and High-Temperature Performance Properties of Warm Mix Asphalt Binders
by Anna Chomicz-Kowalska, Joanna Bartos, Krzysztof Maciejewski and Mateusz M. Iwański
Materials 2023, 16(24), 7648; https://doi.org/10.3390/ma16247648 - 14 Dec 2023
Cited by 1 | Viewed by 1300
Abstract
The present study investigates the effects of the simultaneous use of two additives, an organosilane warm mix asphalt (WMA) agent and a grade-bumping polyolefin compound, on the conventional and high-temperature performance properties of a paving grade 50/70 bitumen and a polymer-modified 45/80-55 bitumen. [...] Read more.
The present study investigates the effects of the simultaneous use of two additives, an organosilane warm mix asphalt (WMA) agent and a grade-bumping polyolefin compound, on the conventional and high-temperature performance properties of a paving grade 50/70 bitumen and a polymer-modified 45/80-55 bitumen. The WMA agent and polyolefin additive were introduced to the binders at rates of up to 0.3% and 2%, respectively. The base asphalt binders and their blends with the additives were tested before and after aging in a rolling thin film oven test at a temperature of 143 °C. The effects of the investigated additives were found to be dependent on the type of base binder and its aging state. It was generally observed that the WMA additive decreased the performance of the asphalt binders and limited the effects of the other additive, which increased the high-temperature stiffness and non-recoverable compliance of the blends. This interaction amounted to as much as an approx. 20% decrease in high-temperature stiffness and non-recoverable compliance of the binders. The additives caused a small increase in the elasticity of the binders and improved their creep performance when measured in multiple stress creep recovery tests. Full article
(This article belongs to the Special Issue Advances in Asphalt Materials (Second Volume))
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17 pages, 5695 KiB  
Article
Methods of Formation of Protective Inhibited Polymer Films on Tungsten
by Natalia A. Shapagina, Alexey V. Shapagin, Vladimir V. Dushik, Andrey A. Shaporenkov, Uliana V. Nikulova, Valentina Yu. Stepanenko, Vladimir V. Matveev, Alexey L. Klyuev and Boris A. Loginov
Int. J. Mol. Sci. 2023, 24(19), 14412; https://doi.org/10.3390/ijms241914412 - 22 Sep 2023
Cited by 1 | Viewed by 1752
Abstract
A comparative study of anticorrosive inhibited polymer films on the tungsten surface formed from an aqueous solution of inhibited formulations (INFOR) containing organosilane and corrosion inhibitors was carried out by means of the prolonged exposure of a tungsten product in a modifying solution [...] Read more.
A comparative study of anticorrosive inhibited polymer films on the tungsten surface formed from an aqueous solution of inhibited formulations (INFOR) containing organosilane and corrosion inhibitors was carried out by means of the prolonged exposure of a tungsten product in a modifying solution and by the method of cataphoretic deposition (CPD). Depending on the method of forming films on tungsten, the molecular organization of the near-surface layers was studied (ATR-FTIR), and the subprimary structure of the films was explored (TEM). The optimal modes of cataphoresis deposition (CPD duration and current density applied to the sample) for the formation of a protective inhibited polymer film on the tungsten surface were established by means of SEM. The energy and thermochemical characteristics (sessile drop and DSC methods), as well as operational (adhesive behavior) and protective filming ability (EIS and corrosion behavior), according to the method of formation of inhibited polymer film, were determined. Based on the combined characteristics of the films obtained by the two methods and the deposition modes, the CPD method showed better performance than the electroless dipping method. Full article
(This article belongs to the Special Issue State-of-the-Art Materials Science in Russia—2nd Edition)
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23 pages, 5465 KiB  
Article
Organosilicon Self-Assembled Surface Nanolayers on Zinc—Formation and Their Influence on the Electrochemical and Corrosion Zinc Ongoing
by Maxim Petrunin, Liudmila Maksaeva and Tatyana Yurasova
Materials 2023, 16(17), 6045; https://doi.org/10.3390/ma16176045 - 2 Sep 2023
Cited by 1 | Viewed by 1468
Abstract
The adsorption of vinyltrimethoxysilane (VS) on the surface of sputtered (by thermal spraying in vacuum) zinc has been investigated. The adsorption isotherms of VC on zinc from an aqueous solution were obtain. In order to determine the adsorption characteristics of VS molecules and [...] Read more.
The adsorption of vinyltrimethoxysilane (VS) on the surface of sputtered (by thermal spraying in vacuum) zinc has been investigated. The adsorption isotherms of VC on zinc from an aqueous solution were obtain. In order to determine the adsorption characteristics of VS molecules and to calculate the heats of adsorption, the obtained adsorption isotherms were mathematically processed in terms of the well-known adsorption approaches (approximations, adsorption isotherms). It has been established that this organosilane was chemisorbed on the surface of freshly deposited zinc after 60 min. After the sample was immersed in the solution, a self-organized organosilicon layer was formed on the metal surface. The application of Fourier transform infrared spectroscopy, atomic-force microscopy, and scanning electron microscopy allowed to us study in detail the interactions between VS molecules and the metal surface and to determine the structural features of the formed surface films. The mechanism of formation of self-assembled surface layers on zinc has been proposed. Electrochemical and corrosion research methods have been used to investigate the anticorrosion characteristics of organosilicon films on zinc. High stability of surface organosilicone layers with respect to the corrosive components of electrolyte action was shown by an infrared spectroscopy study carried out after corrosion tests Full article
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14 pages, 10258 KiB  
Article
Polystyrene Coating on APTES-Primed Hydroxylated AA2024-T3: Characterization and Failure Mechanism of Corrosion
by Cheng-fu Chen
Solids 2023, 4(3), 254-267; https://doi.org/10.3390/solids4030016 - 1 Sep 2023
Cited by 2 | Viewed by 2768
Abstract
Polystyrene has limited adhesivity to inorganic materials such as metals. However, the inorganic surface can be treated to enhance bonding to energetically stable polystyrene. This concept is verified in this paper with organosilane aminopropyltriethoxysilane (APTES) as the coupling agent primed on hydroxylated aluminum [...] Read more.
Polystyrene has limited adhesivity to inorganic materials such as metals. However, the inorganic surface can be treated to enhance bonding to energetically stable polystyrene. This concept is verified in this paper with organosilane aminopropyltriethoxysilane (APTES) as the coupling agent primed on hydroxylated aluminum alloy AA2024-T3. We characterize the structural integrity and electrical impedance of the polystyrene coating on APTES-primed surfaces with different cured conditions after exposure to 3.5 wt.% NaCl solution for seven days. The results show that top-coated polystyrene on APTES is more structurally intact and less electrically conductive than the polystyrene coating alone. The coating layer made of top-coating polystyrene on a curing APTES film has the largest water uptake rate in the early stage of immersion in the corrosion solution. In the later stage, all coating layers tested regained their impedance while losing structural integrity. The charge transfer in the double layer of coated specimens for all types of coatings tested is predominantly through capacitance-based charging/discharging, presumably governed by the adsorption mechanism of ions at the coating/substrate interface. Full article
(This article belongs to the Special Issue Advances in the Study and Application of Polymers)
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18 pages, 2253 KiB  
Review
Application of Electrophoretic Deposition as an Advanced Technique of Inhibited Polymer Films Formation on Metals from Environmentally Safe Aqueous Solutions of Inhibited Formulations
by Natalia A. Shapagina and Vladimir V. Dushik
Materials 2023, 16(1), 19; https://doi.org/10.3390/ma16010019 - 20 Dec 2022
Cited by 9 | Viewed by 3483
Abstract
The presented paper analyzes polymer films formed from aqueous solutions of organosilanes, corrosion inhibitors and their compositions. Methods of depositing inhibited films on metal samples, such as dipping and exposure of the sample in a modifying solution, as well as an alternative method, [...] Read more.
The presented paper analyzes polymer films formed from aqueous solutions of organosilanes, corrosion inhibitors and their compositions. Methods of depositing inhibited films on metal samples, such as dipping and exposure of the sample in a modifying solution, as well as an alternative method, electrophoretic deposition (EPD), are discussed. Information is provided on the history of the EPD method, its essence, production process, areas of application of this technology, advantages over existing analogues, as well as its varieties. The article considers the promise of using the EPD method to form protective inhibited polymer films on metal surfaces from aqueous solutions of inhibitor formulations consisting of molecules of organosilanes and corrosion inhibitors. Full article
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18 pages, 6379 KiB  
Article
Modeling the Properties of Curcumin Derivatives in Relation to the Architecture of the Siloxane Host Matrices
by Florentina Monica Raduly, Valentin Rădiţoiu, Alina Rădiţoiu, Adriana Nicoleta Frone, Cristian Andi Nicolae, Violeta Purcar, Georgiana Ispas, Mariana Constantin and Iuliana Răut
Materials 2022, 15(1), 267; https://doi.org/10.3390/ma15010267 - 30 Dec 2021
Cited by 4 | Viewed by 2328
Abstract
Research in the field of natural dyes has constantly focused on methods of conditioning curcumin and diversifying their fields of use. In this study, hybrid materials were obtained from modified silica structures, as host matrices, in which curcumin dyes were embedded. The influence [...] Read more.
Research in the field of natural dyes has constantly focused on methods of conditioning curcumin and diversifying their fields of use. In this study, hybrid materials were obtained from modified silica structures, as host matrices, in which curcumin dyes were embedded. The influence of the silica network structure on the optical properties and the antimicrobial activity of the hybrid materials was monitored. By modifying the ratio between phenyltriethoxysilane:diphenyldimethoxysilane (PTES:DPDMES), it was possible to evaluate the influence the organosilane network modifiers had on the morphostructural characteristics of nanocomposites. The nanosols were obtained by the sol–gel method, in acid catalysis. The nanocomposites obtained were deposited as films on a glass support and showed a transmittance value (T measured at 550 nm) of around 90% and reflectance of about 11%, comparable to the properties of the uncovered support. For the coatings deposited on PET (polyethylene terephthalate) films, these properties remained at average values of T550 = 85% and R550 = 11% without significantly modifying the optical properties of the support. The sequestration of the dye in silica networks reduced the antimicrobial activity of the nanocomposites obtained, by comparison to native dyes. Tests performed on Candida albicans fungi showed good results for the two curcumin derivatives embedded in silica networks (11–18 mm) by using the spot inoculation method; in comparison, the alcoholic dye solution has a spot diameter of 20–23 mm. In addition, hybrids with the CA derivative were the most effective (halo diameter of 17–18 mm) in inhibiting the growth of Gram-positive bacteria, compared to the curcumin derivative in alcoholic solution (halo diameter of 21 mm). The results of the study showed that the presence of 20–40% by weight DPDMES in the composition of nanosols is the optimal range for obtaining hybrid films that host curcumin derivatives, with potential uses in the field of optical films or bioactive coatings. Full article
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17 pages, 2810 KiB  
Article
Role of Surface Preparation in Corrosion Resistance Due to Silane Coatings on a Magnesium Alloy
by Abhishek Saxena and R. K. Singh Raman
Molecules 2021, 26(21), 6663; https://doi.org/10.3390/molecules26216663 - 3 Nov 2021
Cited by 9 | Viewed by 2301
Abstract
Coating of an organo-silane (Bis-1,2-(TriethoxySilyl)Ethane (BTSE)) has been observed to improve the corrosion resistance of magnesium alloy AZ91D. Three different types of surface preparations have been employed before condensing the silane coating on to the substrate. Corrosion resistance was investigated using electrochemical impedance [...] Read more.
Coating of an organo-silane (Bis-1,2-(TriethoxySilyl)Ethane (BTSE)) has been observed to improve the corrosion resistance of magnesium alloy AZ91D. Three different types of surface preparations have been employed before condensing the silane coating on to the substrate. Corrosion resistance was investigated using electrochemical impedance spectroscopy (EIS). A specific alkali treatment of the substrate prior to the coating has been found to improve the corrosion resistance of the coated alloy, which has been attributed to the ability of the treatment in facilitating the condensation of a relatively compact siloxane film. Full article
(This article belongs to the Special Issue Electrochemistry and Corrosion Protection of Metallic Materials)
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14 pages, 7473 KiB  
Article
Adsorption of Organosilanes on the Surface of Aluminium and the Formation of Organosilane Films to Protect It from Corrosion
by Natalia Gladkikh, Maxim Petrunin, Ludmila Maksaeva and Tatyana Yurasova
Materials 2021, 14(19), 5757; https://doi.org/10.3390/ma14195757 - 2 Oct 2021
Cited by 11 | Viewed by 2061
Abstract
Adsorption of diaminesilane (DAS), vinyltrimethoxysilane (VS) on the surface of thermally precipitated aluminium was examined. The use of different adsorption isotherms made it possible to calculate the adsorption heats for DAS and VS. It was determined that chemisorption of these organosilanes occurred on [...] Read more.
Adsorption of diaminesilane (DAS), vinyltrimethoxysilane (VS) on the surface of thermally precipitated aluminium was examined. The use of different adsorption isotherms made it possible to calculate the adsorption heats for DAS and VS. It was determined that chemisorption of these organosilanes occurred on the surface of aluminium. Exposure of aluminium for 60 min to aqueous solutions of organosilanes led to the formation of organosilane films on the surface of the metal. The use of infrared spectroscopy and scanning electron microscopy in the work made it possible to assess the interactions of organosilanes with the metal surface, as well as to determine the structural features of the films and their thickness. Electrochemical and corrosion research methods made it possible to study the protective properties of organosilane films on aluminium. Full article
(This article belongs to the Special Issue Corrosion Prediction and Corrosion Protection)
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16 pages, 15668 KiB  
Article
Role of Functional Monomers upon the Properties of Bisphenol A Molecularly Imprinted Silica Films
by Ana-Mihaela Gavrila, Ionut-Cristian Radu, Hermine Stroescu, Anamaria Zaharia, Elena-Bianca Stoica, Ana-Lorena Ciurlica, Tanţa-Verona Iordache and Andrei Sârbu
Appl. Sci. 2021, 11(7), 2956; https://doi.org/10.3390/app11072956 - 25 Mar 2021
Cited by 4 | Viewed by 2470
Abstract
In this study, two types of bisphenol A molecularly imprinted films (BPA-MIP) were successfully prepared via sol-gel derived methods using two different organosilane functional monomers N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (DAMO-T) or (3-mercaptopropyl)trimethoxysilane (MPTES). The physical-chemical characterization of films, in terms of morphology, structure, thermal analysis, and [...] Read more.
In this study, two types of bisphenol A molecularly imprinted films (BPA-MIP) were successfully prepared via sol-gel derived methods using two different organosilane functional monomers N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (DAMO-T) or (3-mercaptopropyl)trimethoxysilane (MPTES). The physical-chemical characterization of films, in terms of morphology, structure, thermal analysis, and optical features, suggested that thinner films with a homogenous porous structure were more likely to retain BPA molecules. The MIP films revealed the rapid and quantitative adsorption of BPA, registering the most specific binding in the first five minutes of contact with the BPA-MIP film. Silica films were effectively regenerated for further usage for at least five times, demonstrating their high stability and reusability. Even if the performance of films for BPA uptake dropped dramatically after the third adsorption/reconditioning cycle, this synthesis method for BPA-MIP films has proven to be a reliable and cheap way to prepare sensitive films with potential application for re-usable optical sensors. Full article
(This article belongs to the Special Issue Applications of Molecularly Imprinted Films)
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14 pages, 5153 KiB  
Article
A Process for the Synthesis and Use of Highly Aromatic Organosilanes as Additives for Poly(Vinyl Chloride) Films
by Safaa H. Mohamed, Ayad S. Hameed, Gamal A. El-Hiti, Dina S. Ahmed, Mohammed Kadhom, Mohammed A. Baashen, Muna Bufaroosha, Ahmed A. Ahmed and Emad Yousif
Processes 2021, 9(1), 91; https://doi.org/10.3390/pr9010091 - 4 Jan 2021
Cited by 21 | Viewed by 2833
Abstract
Three organosilanes were synthesized in good yields from the condensation of 4,4′,4″-((phenylsilanetriyl)tris(oxy))tribenzaldehyde and 4-substituted anilines under acidic conditions. The structure of the organosilanes was confirmed using a variety of techniques. Organosilanes were mixed with poly(vinyl chloride) (PVC) and homogenous films were produced. The [...] Read more.
Three organosilanes were synthesized in good yields from the condensation of 4,4′,4″-((phenylsilanetriyl)tris(oxy))tribenzaldehyde and 4-substituted anilines under acidic conditions. The structure of the organosilanes was confirmed using a variety of techniques. Organosilanes were mixed with poly(vinyl chloride) (PVC) and homogenous films were produced. The effect of long-term irradiation on the films containing organosilanes was tested using various methods. Monitoring the infrared spectra of PVC films before, during and after irradiation processes showed the formation of side products comprising polyene, carbonyl and hydroxyl groups. The intensities of absorption bands due to these functional groups were much lower in the presence of organosilanes as compared to the blank film. Also, the decrease in the weight and molecular weight of PVC films after irradiation was lower in the presence of organosilanes. Additionally, there was a minimal surface change of irradiated PVC in the presence of organosilanes. Clearly, organosilanes act as inhibitors, particularly the one containing the hydroxyl group, for the photodegradation of PVC. Different mechanisms were proposed to speculate the role played by organosilanes in stabilizing PVC against long-term ultraviolet light exposure. Full article
(This article belongs to the Section Chemical Processes and Systems)
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14 pages, 1989 KiB  
Article
Montecarlo Simulation and HAXPES Analysis of Organosilane Segregation in Titania Xerogel Films; Towards a Generic Surface Chemofunctionalization Process
by Javier Mateo Moreno, Rodrigo Calvo Membibre, Sergio Pinilla Yanguas, Juan Rubio Zuazo and Miguel Manso Siván
Surfaces 2020, 3(3), 352-365; https://doi.org/10.3390/surfaces3030026 - 28 Jul 2020
Cited by 2 | Viewed by 2961
Abstract
The formation of xerogels implies a sequence of hydrolysis and condensation reactions, which are intricate to analyze in heteromolecular sols. We analyze by probabilistic Montecarlo methods the development of hybrid organosilane–titania xerogels and illustrate how partial charges of the reacting molecules can help [...] Read more.
The formation of xerogels implies a sequence of hydrolysis and condensation reactions, which are intricate to analyze in heteromolecular sols. We analyze by probabilistic Montecarlo methods the development of hybrid organosilane–titania xerogels and illustrate how partial charges of the reacting molecules can help estimating relative probabilities for the condensation of the molecules. Since the condensation rate of Ti alkoxides is much higher than the corresponding rate of Si alkoxides (especially if bearing a non-hydrolizable group), by imposing a fast condensation process in agreement with low pH kinetics, the process leads to a surface segregation of the organosilane. The simulation results are compared with results of characterization of thin condensates of two different organosilanes within a titanium–isopropoxide matrix. Non-destructive in-depth profiles were obtained by hard x-ray photoelectron spectroscopy, which can resolve through estimation of Si and specific moieties of the organosilane molecules the progress of the condensation. These results are relevant for the generalization of chemo-functionalization processes by kinetic demixing of organosilanes, which have myriad applications in biomedicine and biotechnology. Full article
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17 pages, 3054 KiB  
Article
Impact of Surface Chemistry and Doping Concentrations on Biofunctionalization of GaN/Ga‒In‒N Quantum Wells
by Nilanjon Naskar, Martin F. Schneidereit, Florian Huber, Sabyasachi Chakrabortty, Lothar Veith, Markus Mezger, Lutz Kirste, Theo Fuchs, Thomas Diemant, Tanja Weil, R. Jürgen Behm, Klaus Thonke and Ferdinand Scholz
Sensors 2020, 20(15), 4179; https://doi.org/10.3390/s20154179 - 28 Jul 2020
Cited by 3 | Viewed by 4335
Abstract
The development of sensitive biosensors, such as gallium nitride (GaN)-based quantum wells, transistors, etc., often makes it necessary to functionalize GaN surfaces with small molecules or even biomolecules, such as proteins. As a first step in surface functionalization, we have investigated silane adsorption, [...] Read more.
The development of sensitive biosensors, such as gallium nitride (GaN)-based quantum wells, transistors, etc., often makes it necessary to functionalize GaN surfaces with small molecules or even biomolecules, such as proteins. As a first step in surface functionalization, we have investigated silane adsorption, as well as the formation of very thin silane layers. In the next step, the immobilization of the tetrameric protein streptavidin (as well as the attachment of chemically modified iron transport protein ferritin (ferritin-biotin-rhodamine complex)) was realized on these films. The degree of functionalization of the GaN surfaces was determined by fluorescence measurements with fluorescent-labeled proteins; silane film thickness and surface roughness were estimated, and also other surface sensitive techniques were applied. The formation of a monolayer consisting of adsorbed organosilanes was accomplished on Mg-doped GaN surfaces, and also functionalization with proteins was achieved. We found that very high Mg doping reduced the amount of surface functionalized proteins. Most likely, this finding was a consequence of the lower concentration of ionizable Mg atoms in highly Mg-doped layers as a consequence of self-compensation effects. In summary, we could demonstrate the necessity of Mg doping for achieving reasonable bio-functionalization of GaN surfaces. Full article
(This article belongs to the Special Issue Thin-Film Materials and Nanostructure Devices Applicable for Sensing)
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14 pages, 4286 KiB  
Article
Monitoring Silane Sol-Gel Kinetics with In-Situ Optical Turbidity Scanning and Dynamic Light Scattering
by Abul Bashar Mohammad Giasuddin and David W. Britt
Molecules 2019, 24(16), 2931; https://doi.org/10.3390/molecules24162931 - 13 Aug 2019
Cited by 10 | Viewed by 6024
Abstract
Organosilanes (e.g., R’-SiOR3) provide hydrophobic functionality in thin-film coatings, porous gels, and particles. Compared with tetraalkoxysilanes (SiOR4), organosilanes exhibit distinct reaction kinetics and assembly mechanisms arising from steric and electronic properties of the R’ group on the silicon atom. [...] Read more.
Organosilanes (e.g., R’-SiOR3) provide hydrophobic functionality in thin-film coatings, porous gels, and particles. Compared with tetraalkoxysilanes (SiOR4), organosilanes exhibit distinct reaction kinetics and assembly mechanisms arising from steric and electronic properties of the R’ group on the silicon atom. Here, the hydrolysis and condensation pathways of n-propyltrimethoxy silane (nPM) and a tri-fluorinated analog of nPM, 3,3,3-trifluoropropyl trimethoxy silane (3F), were investigated under aqueous conditions at pH 1.7, 2.0, 3.0, and 4.0. Prior to hydrolysis, 3F and nPM are insoluble in water and form a lens at the bottom (3F) or top (nPM) of the solutions. This phase separation was employed to follow reaction kinetics using a Turbiscan instrument to monitor hydrolysis through solubilization of the neat silane lens while simultaneously tracking condensation-induced turbidity throughout the bulk solution. Dynamic light scattering confirmed the silane condensation and particle aggregation processes reported by the turbidity scanning. Employing macroscopic phase separation of the starting reactants from the solvent further allows for control over the reaction kinetics, as the interfacial area can be readily controlled by reaction vessel geometry, namely by controlling the surface area to volume. In-situ turbidity scanning and dynamic light scattering revealed distinct reaction kinetics for nPM and 3F, attributable to the electron withdrawing and donating nature of the fluoro- and organo-side chains of 3F and nPM, respectively. Full article
(This article belongs to the Special Issue Sol-Gel Chemistry. From Molecule to Functional Materials)
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10 pages, 1346 KiB  
Article
The Role of Physisorption and Chemisorption in the Oscillatory Adsorption of Organosilanes on Aluminium Oxide
by Ruby A. Sims, Sarah L. Harmer and Jamie S. Quinton
Polymers 2019, 11(3), 410; https://doi.org/10.3390/polym11030410 - 4 Mar 2019
Cited by 63 | Viewed by 7577
Abstract
The effect of physisorbed and chemisorbed species on the time-dependent self-assembly mechanism of organosilane films has been investigated on aluminium oxide using X-ray Photoelectron Spectroscopy. The role of physisorbed species was determined through their removal using a simple rinsing procedure while monitoring film [...] Read more.
The effect of physisorbed and chemisorbed species on the time-dependent self-assembly mechanism of organosilane films has been investigated on aluminium oxide using X-ray Photoelectron Spectroscopy. The role of physisorbed species was determined through their removal using a simple rinsing procedure while monitoring film substrate coverage. Removing physisorbed species from Propyldimethylmethoxysilane films, shown to follow a Langmuir-type adsorption profile, reduces the substrate coverage initially but quickly results in coverages equivalent to films that did not undergo a rinsing procedure. This indicates that all Propyldimethylmethoxysilane molecules are covalently bound to the substrate following 15 s of film growth. Removing physisorbed species from films, which have been shown to follow an oscillatory adsorption profile, Propyltrimethoxysilane and Propylmethyldimethoxysilane, reveal the persistence of these oscillations despite a reduction in silane substrate coverage. These results not only confirm the presence of two thermodynamically favourable phases in the condensation equilibrium reaction as physisorbed and chemisorbed species, but also indicate that the desorption of species during film growth involves both states of chemical binding. Full article
(This article belongs to the Special Issue Nanotechnology of Polymers and Biomaterials)
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14 pages, 5508 KiB  
Article
Visible Light Assisted Organosilane Assembly on Mesoporous Silicon Films and Particles
by Chloé Rodriguez, Alvaro Muñoz Noval, Vicente Torres-Costa, Giacomo Ceccone and Miguel Manso Silván
Materials 2019, 12(1), 131; https://doi.org/10.3390/ma12010131 - 3 Jan 2019
Cited by 8 | Viewed by 4130
Abstract
Porous silicon (PSi) is a versatile matrix with tailorable surface reactivity, which allows the processing of a range of multifunctional films and particles. The biomedical applications of PSi often require a surface capping with organic functionalities. This work shows that visible light can [...] Read more.
Porous silicon (PSi) is a versatile matrix with tailorable surface reactivity, which allows the processing of a range of multifunctional films and particles. The biomedical applications of PSi often require a surface capping with organic functionalities. This work shows that visible light can be used to catalyze the assembly of organosilanes on the PSi, as demonstrated with two organosilanes: aminopropyl-triethoxy-silane and perfluorodecyl-triethoxy-silane. We studied the process related to PSi films (PSiFs), which were characterized by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF-SIMS) and field emission scanning electron microscopy (FESEM) before and after a plasma patterning process. The analyses confirmed the surface oxidation and the anchorage of the organosilane backbone. We further highlighted the surface analytical potential of 13C, 19F and 29Si solid-state NMR (SS-NMR) as compared to Fourier transformed infrared spectroscopy (FTIR) in the characterization of functionalized PSi particles (PSiPs). The reduced invasiveness of the organosilanization regarding the PSiPs morphology was confirmed using transmission electron microscopy (TEM) and FESEM. Relevantly, the results obtained on PSiPs complemented those obtained on PSiFs. SS-NMR suggests a number of siloxane bonds between the organosilane and the PSiPs, which does not reach levels of maximum heterogeneous condensation, while ToF-SIMS suggested a certain degree of organosilane polymerization. Additionally, differences among the carbons in the organic (non-hydrolyzable) functionalizing groups are identified, especially in the case of the perfluorodecyl group. The spectroscopic characterization was used to propose a mechanism for the visible light activation of the organosilane assembly, which is based on the initial photoactivated oxidation of the PSi matrix. Full article
(This article belongs to the Special Issue Surface Modification to Improve Properties of Materials)
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