Sessile Drop Water Contact Angle Research Articles

Thermal degradation behavior of self-assembled monolayer surfactant on silicon substrate

In nanoimprint lithography, a release agent on the mold surface is usually necessary for easy demolding between the mold and the imprinted (thermal) resist. In this work, the thermal stability of 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS) monolayers is studied using x-ray photoelectron spectroscopy. The FDTS monolayers are deposited on Si (100) substrates via vapor phase reactions. Significant fluorine desorption of the monolayers is observed for samples annealed at 250 and 300 °C in air. The fluorine coverage decreases as a function of annealing time at a given annealing temperature. The desorption is proposed to be dependent on the monolayer packing details and may be influenced by the intermolecular heat transfer. Removal of the CF3 groups is found to be faster than that of the CF2 group as evidenced by the CF2/CF3 peak area ratios that increase with the annealing time. Sessile drop water contact angle and fluorine coverage evolution results show that the estimated useful coating lifetime is 180 min when the samples are annealed at 300 °C and ∼560 min when annealed at 250 °C. The peak position of the binding energy of the F 1s spectral line is related to the monolayer fluorine coverage and it may be a result of the interactions between the molecular chain and the negatively charged silicon substrate. Furthermore, nearly no chain desorption is detected for samples annealed in an inert environment, which may be attributed to the elimination of reactive oxygen and moisture molecules. The thermal degradation behaviors in ambient and inert atmosphere provide useful information for designing a nanoimprint process for the commercial manufacturing of polymeric microstructure and nanostructure.

Vapor-Phase Plotting of Organosilane Chemical Gradients.

Vapor-phase plotting of organosilane-based self-assembled monolayer (SAM) gradients is demonstrated for the first time. Patterned SAMs are formed by delivering gas-phase organotrichlorosilane precursors to a reactive silica surface using a heated glass capillary. The capillary is attached via a short flexible tube to a reservoir containing the precursor dissolved in toluene. The proximal end of the capillary is positioned at an experimentally optimized distance of 30 μm above the substrate during film deposition. The capillary is mounted to a stepper-motor-driven X, Y plotter for raster scanning above the surface. Two different organotrichlorosilane precursors are employed in this initial demonstration: n-octyltrichlorosilane and 3-cyanopropyltrichlorosilane. The dependence of SAM deposition on ambient relative humidity, capillary-substrate separation, raster-scanning speed, and solvent viscosity and volatility is explored and optimum deposition conditions are identified. The optimized procedures are used to plot uniformly modified square "pads" and gradients of the silanes. Film formation is verified and the gradient profiles are obtained by sessile drop water contact angle measurements, spectroscopic ellipsometry measurements of film thickness, and X-ray photoelectron spectroscopy mapping. The resolution of the plotting process is currently in the millimeter range and depends on capillary diameter and distance from the substrate surface. Vapor-phase plotting affords a unique direct-write method for producing patterned and chemically graded SAMS that may find applications in microfluidic devices, planar chromatography, and optical and electronic devices.

Single Molecule Catch and Release: Potential-Dependent Plasmid DNA Adsorption along Chemically Graded Electrode Surfaces.

Single molecule detection methods were employed to study the potential dependent adsorption and desorption of dye labeled plasmid DNA along chemical gradients prepared on indium tin oxide (ITO) electrodes. Gradients were formed over silica-base-layer-coated ITO surfaces by exposing them in a directional fashion to aminopropyltrimethoxysilane from the vapor phase. Sessile drop water contact angle measurements, spectroscopic ellipsometry, and X-ray photoelectron spectroscopy were used to verify that a gradient was formed and to characterize its wettability, thickness, and composition as a function of position. The gradient-coated ITO electrode served as both the working electrode and a window into the electrochemical cell used to manipulate DNA adsorption. For single molecule studies, the electrochemical cell was filled with buffer solution containing YOYO-1-labeled plasmid DNA. Fluorescence videos acquired along the gradients depicted clear position-, potential-, and pH-dependent variations in DNA adsorption and desorption. The results demonstrate that DNA adsorption was largely independent of applied potential and irreversible at high amine coverage (i.e., multilayers), under pH ∼ 6 buffer. DNA adsorption became more reversible as the amine coverage decreased and the solution pH increased. Potential dependent control over DNA adsorption and desorption was best achieved at monolayer-to-submonolayer aminosilane coverage under pH ∼ 8 buffer. The knowledge gained in these studies will aid in the development of electrochemical methods for the capture and release of DNA and other polyelectrolytes at electrode surfaces.

Nanocoating on alkali-resistant glass fibers by octadecyltrichlorosilane to improve the mechanical strength of fibers and fibers/epoxy composites

Surface defects cause the measured tensile strength of alkali glass fibers to be significantly lower than their theoretical values. Coatings can be used to “heal” surface flaws and to modify surface properties. In the present work, the nanocoating on alkali-resistant glass (ARG) fiber rovings was carried out by self-assembled monolayers (SAMs) of octadecyltrichlorosilane (OTS). The ARG roving was dipped into OTS nanosol, which deposited the organic–inorganic SAMs of OTS on the ARG surface. The assessment of changes in the fiber surfaces was characterized by scanning electron microscopy (SEM) and fluorescence microscopy, while the chemical changes were characterized by X-ray photoelectron spectroscopy (XPS). Furthermore, the influence of nanocoating on the tensile properties of ARG and OTS-treated ARG with and without an epoxy matrix was also studied. The SEM analysis revealed the formation of nanoscale layers on the ARG surfaces and the XPS confirmed the deposition of organic–inorganic monolayers. The tensile strength of ARG rovings with and without the epoxy matrix was improved significantly. The OTS treatment almost created a superhydrophobic nanocoating on ARG, which was confirmed by the sessile drop water contact angle, and the water absorption by the ARG/epoxy composites reduced.

Wet Chemical Functionalization of GaP(111)B through a Williamson Ether-Type Reaction

Functionalization of crystalline gallium phosphide (GaP) (111)B interfaces has been performed through the formation of P–O–R surface bonds. The approach described herein parallels classical Williamson ether synthesis, where hydroxyl groups on etched GaP(111)B surfaces were reacted with halogenated reactants. Grazing angle total internal reflectance infrared spectra showed increased intensities for −CH2– and −CH3 asymmetric and symmetric stretches after reaction with long alkyl halides. Changes in the X-ray photoelectron spectra collected before and after reaction separately corroborated surface attachment to GaP(111)B. Static sessile drop water contact angle measurements for GaP(111)B separately showed increased hydrophobicity following surface modification with long alkyl chains. The surface functionalization reaction rate was increased by the addition of non-nucleophilic bases, consistent with surface deprotonation as the rate-limiting step. Separately, photoelectrochemical measurements conducted before and after reaction with alkyl halides at long wavelengths (λ > 545 nm) showed surface attachment decreased sub-band-gap photocurrents, implying lowered activity of surface traps. Conversely, photoelectrochemical measurements performed after functionalization of p-GaP(111)B with Coomassie Blue sulfonyl chloride showed evidence of persistent sensitized hole injection from the dye into p-GaP.

Single-Molecule Spectroscopic Imaging Studies of Polarity Gradients Prepared by Infusion-Withdrawal Dip-Coating

Sol–gel-derived thin films incorporating a one-dimensional polarity gradient are prepared by infusion-withdrawal dip-coating (IWDC) and characterized by single-molecule spectroscopic (SMS) imaging. Nonpolar phenyltrimethoxysilane (PTMOS) and polar tetramethoxysilane (TMOS) are used as precursor silanes during IWDC. Sessile drop water contact angle measurements demonstrate the presence of a wettability gradient in the resulting films, on macroscopic length scales. Raman maps of the phenyl C–H stretch at 3059 cm–1 confirm gradient formation. Material polarity is assessed by SMS imaging, using Nile Red as a polarity-sensitive probe. Polarity data are obtained by recording fluorescence videos of single-molecule emission simultaneously in two spectral bands (590 ± 20 and 640 ± 20 nm). The pairs of fluorescence spots produced by each molecule are identified and analyzed using automated spot-tracking software. The local film polarity is quantified via the Clausius–Mossotti factors calculated from the single-mole...

In-vitro wettability of four silicone hydrogel lenses with differing surface properties

Purpose: To determine and compare the advancing sessile drop water contact angles (CAs) of four silicone hydrogel (SH) materials which utilise differing approaches to enhance wettability. These included a material that is plasma oxidized (balafilcon A), one with a plasma coating (lotrafilcon B), one with an internal wetting agent (senofilcon and also an untreated/unmodified material (comfilcon A).

Immobilization of [60]fullerene on silicon surfaces through a calix[8]arene layer

In this work, we report the functionalization of flat Si(100) surfaces with a calix[8]arene derivative through a thermal hydrosilylation process, followed by docking with [60]fullerene. Chemical grafting of calix[8]arene on silicon substrates was evaluated by X-ray photoelectron spectroscopy, whereas host-guest immobilization of fullerene was demonstrated by atomic force microscopy and sessile drop water contact angle measurements. Surface topographical variations, modelled on the basis of calix[8]arene and [60]fullerene geometrical parameters, are consistent with the observed morphological features relative to surface functionalization and to non-covalent immobilization of [60]fullerene.

A silver nanocomposite biomaterial for blood‐contacting implants

Cardiovascular implants must resist infection and thrombosis. A nanocomposite polymeric material [polyhedral-oligomeric-silsesquioxane-poly(carbonate-urea)urethane; POSS-PCU] demonstrates ideal properties for cardiovascular applications. Silver nanoparticles or nanosilver (NS) are recognized for efficient antibacterial properties. This study aims to determine the influence of NS integrated POSS-PCU on thrombogenicity. Silver nitrate was reduced with dimethylformamide and stabilized by the inclusion of fumed silica nanoparticles to prevent aggregation of NS and were incorporated into POSS-PCU to form a range of POSS-PCU-NS concentrations (by weight); 0.20% (NS16), 0.40% (NS32), 0.75% (NS64), and 1.50% (NS128). Surface wettability was determined with sessile-drop water contact angles. Platelets were introduced onto test samples and Alamar Blue (AB), mitochondrial-activity assay, quantified the degree of platelet adhesion whilst platelet-factor-4 (PF4) ELISA quantified the degree of platelet activation. Thromboelastography (TEG) determined the profiles of whole blood kinetics while hemolysis assay demonstrated the degree of blood compatibility. Increasing levels of NS induced greater hydrophilicity. A concentration dependant decrease in platelet adhesion and activation was observed with AB and PF4 readings, respectively. TEG demonstrated that the antithrombogenic properties of POSS-PCU were retained with POSS-PCU-NS16, and enhanced with POSS-PCU-NS32, but was reduced with POSS-PCU-NS64 and POSS-PCU-NS128. POSS-PCU-NS64 and POSS-PCU-NS128 demonstrated a hemolytic tendency, but no hemolysis was observed with POSS-PCU-NS16 and POSS-PCU-NS32. Overall, POSS-PCU-NS32 rendered potent antithrombogenic properties.

Surface characterisation of PET modified using a p‐DC or HIPIMS reactive sputter pre‐treatment

Surface‐sensitive techniques have been employed to characterise a model polymer substrate surface, poly(ethylene terephthalate) (PET), after a reactive sputter pre‐treatment using magnetically enhanced Cu or Ti sputter targets in a mixed Ar‐O2 glow discharge plasma. The plasmas are produced using either medium‐frequency pulsed direct current (p‐DC) or low‐frequency high power impulse (HIPIMS) sources. X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and sessile drop water contact angles were employed to investigate changes in PET surface chemistry and properties following surface modification using different p‐DC and HIPIMS process parameters.The XPS results indicate that the chemical composition of plasma‐treated PET surfaces (p‐DC or HIPIMS) depends strongly on the processing parameters employed such as sputter target material, magnetic array type and power supply technology. XPS results demonstrate that the sputter target material employed is of primary importance as it dictates the quantity of metal deposited/implanted into the PET surface. XPS results show that the use of a Cu target resulted in ~ 31–35 at.% of Cu incorporated into the PET surface (as CuO), while the use of a Ti target resulted in only 1–4 at. % incorporation (as TiO2). The SIMS spectra and XPS depth profiles of Cu‐treated PET indicate that the CuO has formed a discrete film at the surface, offering predominant or total coverage of the underlying PET. However, for Ti‐treated PET, both PET and Ti SIMS peaks are observed, and the XPS C1s peak shape is characteristic of PET, indicating that Ti has not formed a discrete film, but instead TiO2 species have been incorporated, probably as an island‐like distribution into the surface of the PET. The formation of CuO and TiO2 on the PET surface leads to a reduction in the contact angle compared to native PET. Hence, both p‐DC and HIPIMS reactive plasma pre‐treatments result in a more hydrophilic surface, promoting adhesion and offering a flexible means to introduce a wide range of surface chemistries and properties to polymeric surfaces. Copyright © 2012 John Wiley & Sons, Ltd.

A comparison of reactive plasma pre-treatments on PET substrates by Cu and Ti pulsed-DC and HIPIMS discharges

PET web samples have been treated by magnetically enhanced glow discharges powered using either medium frequency pulse direct current (p-DC) or low frequency high power pulse (HIPIMS) sources. The plasma pre-treatment processes were carried out in an Ar–O 2 atmosphere using either Cu or Ti sputter targets. XPS, AFM and sessile drop water contact angle measurements have been employed to examine changes in surface chemistry and morphology for different pre-treatment process parameters. Deposition of metal oxide onto the PET surface is observed as a result of the sputter magnetron-based glow discharge web treatment. Using the Cu target, both the p-DC and HIPIMS processes result in the formation of a thin CuO layer (with a thickness between 1 and 11 nm) being deposited onto the PET surface. Employing the Ti target, both p-DC and HIPIMS processes give rise to a much lower concentration of Ti (< 5 at.%), in the form of TiO 2 on the PET treated surface. The TiO 2 is probably distributed as an island-like distribution covering the PET surface. Presence of Cu and Ti oxide constituents on the treated PET is beneficial in aiding the adhesion but alone (i.e. without oxygen plasma activation) is not enough to provide very high levels of hydrophilicity as is clear from sessile drop water contact angle measurements on aged samples. Exposure to the plasma treatments leads to a small amount of roughening of the substrate surface, but the average surface roughness in all cases is below 2.5 nm. The PET structure at the interface with a coating is mostly or wholly preserved. The oxygen plasma treatment, metal oxide deposition and surface roughening resulting from the HIPIMS and p-DC treatments will promote adhesion to any subsequent thin film that is deposited immediately following the plasma treatment.

SURFACE CHARACTERIZATION AND HEMOCOMPATIBILITY OF HEPARINIZED 316L STAINLESS STEEL

Poor compatibility between blood and metallic coronary artery stents is one reason for arterial restenosis. Immobilization of heparin on stent's surface is feasible for improving compatibility. We examined possible surface-coupling agents for anticoagulant agent immobilization. Hexamethylene diisocyanate (HMDI) was examined as surface-coupling agent to activate 316L stainless steel (e.g. stent material). Afterwards, we grafted PEG on the HMDI activated surface to provide heparin with higher conformational freedom and a more hydrophilic environment. The effectiveness of HMDI activated and PEG grafted surface was confirmed by FTIR, XPS, and water contact angle test. Heparin was then immobilized onto the activated 316L stainless steel. The heparin surface density was 9.5 μg/cm2. Sessile drop water contact angles showed that the heparingrafted surface is even more hydrophilic than the PEG grafted one. The function of grafted heparin was evaluated by antithrombrin III (ATIII) adsorption testing and SEM. The surface with heparin grafting shows better ATIII binding ability and hemocompatibility than the native one.

SURFACE CHARACTERIZATION AND HEMOCOMPATIBILITY OF HEPARINIZED 316L STAINLESS STEEL

Poor compatibility between blood and metallic coronary artery stents is one reason for arterial restenosis. Immobilization of heparin on stent's surface is feasible for improving compatibility. We examined possible surface-coupling agents for anticoagulant agent immobilization. Hexamethylene diisocyanate (HMDI) was examined as surface-coupling agent to activate 316L stainless steel (e.g. stent material). Afterwards, we grafted PEG on the HMDI activated surface to provide heparin with higher conformational freedom and a more hydrophilic environment. The effectiveness of HMDI activated and PEG grafted surface was confirmed by FTIR, XPS, and water contact angle test. Heparin was then immobilized onto the activated 316L stainless steel. The heparin surface density was 9.5 μg/cm2. Sessile drop water contact angles showed that the heparingrafted surface is even more hydrophilic than the PEG grafted one. The function of grafted heparin was evaluated by antithrombrin III (ATIII) adsorption testing and SEM. The surface with heparin grafting shows better ATIII binding ability and hemocompatibility than the native one.

Fabrication of hydrophobic fluorinated amorphous carbon thin films by an electrochemical route

A novel electrochemical route for the preparation of hydrophobic fluorinated amorphous carbon (a-C:F) films with nanostructured surfaces on single crystal silicon substrate was reported. The films were investigated in terms of the surface morphology, chemical composition, microstructure and hydrophobic behavior. The results showed that a highly uniform and densely packed bamboo shoot-like nanostructure was obtained without any use of template. The incorporation of fluorine presented mainly in the forms of CF 2 chains and C CF x ( x = 1, 2) in the films. Sessile drop water contact angle measurements showed that the contact angle of a-C:F films deposited by electrochemical route was about 145°, which can be attributed to the lower surface energy of CF x groups and higher diffusion resistance of the special nanostructured surface to water. Moreover, the related growth mechanism of the resulting films in liquid-phase electrodeposition is discussed as well.

Immobilization of heparin on a silicone surface through a heterobifunctional PEG spacer

A novel method of immobilizing heparin on a silicone surface through a heterobifunctional PEG spacer was used yield well defined surfaces with highly active surface immobilized heparin and low non-specific protein adsorption. The heparin surface density achieved using this technique was 0.68 μg/cm 2. Sessile drop water contact angles showed increased hydrophilicity of the silicone surface after PEG modification and a further decrease in the contact angles following the grafting of heparin. High specificity for ATIII with little fibrinogen adsorption was noted in plasma adsorption studies. This ATIII adsorption was mediated by the heparin layer, since surfaces modified with PEG only did not adsorb significant quantities of AT. The thrombin resistance of the heparin modified surfaces was demonstrably greater as measured by a chromogenic thrombin generation assay. The results suggest that the heterbifunctional PEG linker results in a high density of active heparin on the surfaces.

2-Methacryloyloxyethyl N-butylcarbamate: a new co-monomer for synthesis of polyurethane hydrogels with improved mechanical properties for biomedical applications

Hydrogels with tunable hydrophilic and mechanical properties were synthesized by the free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) and 2-methacryloyloxyethyl N-butylcarbamate. The resulting hydrogels were investigated for their equilibrium water content, sessile drop water contact angles, gel fraction, mechanical properties and protein adsorption. Results indicated that co-polymer hydrogels have good hydrophilicity and that, with the incorporation of the 2-methacryloyloxyethyl N-butylcarbamate, mechanical properties could be improved significantly without affecting other important properties. Lysozyme and albumin adsorption experiments demonstrated that, similar to most hydrogel materials, the co-polymer hydrogels adsorb more lysozyme than albumin and that the adsorption was dependent on hydrophilicity. The control poly(HEMA) hydrogels were found to adsorb more protein than the co-polymer hydrogels; this is thought to be primarily a consequence of protein absorption rather than protein adsorption.

Comparative study of self‐assembly of a range of monofunctional aliphatic molecules on magnetron‐sputtered aluminium

AbstractThe adsorption of a range of organic molecules from toluene onto the oxidized surface of magnetron‐sputtered aluminium metal is studied using sessile drop water contact angle measurements. Molecules with different head group functionalities and various chain lengths are considered, including alkyl carboxylic acids, alkyl phosphonic acids, alkyl amines, alkyl trimethoxysilanes, alkyl trichlorosilanes and epoxy alkanes. Alkyl phosphonic and carboxylic acids are identified as readily forming the most well‐packed monolayers on the aluminium surface, whereas the others adsorb less well and the chlorosilanes polymerize as a result of combination with moisture to form a thick deposit. The high‐adsorption‐density monolayers of alkyl phosphonic and carboxylic acids were studied using polarization modulation infrared reflection–absorption spectroscopy (PM‐IRRAS) and x‐ray photoelectron spectroscopy (XPS): PM‐IRRAS reveals relatively poorer ordering of the C10 alkyl carboxylic acid monolayer compared with that formed from the phosphonic acid, and XPS data suggest that this is likely to relate to a lower ability to displace preadsorbed volatile organic compounds. Copyright © 2004 John Wiley &amp; Sons, Ltd.

Vapor-Phase Adsorption Kinetics of 1-Decene on H-Terminated Si(100)

We have investigated in situ and in real time vapor-phase self-assembly of 1-decene on Si, using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIRS). The adsorption of 1-decene on hydrogenated Si(100) results in a decane-terminated hydrophobic surface, indicated by the sessile-drop water contact angle at 107 ± 2°. This maximum contact angle is achieved at 160 °C under 30 mTorr of vapor-phase 1-decene. The fractional surface coverage of decane, calculated from the IR absorbance of C−H stretching vibrational modes near 2900 cm-1, follows a Langmuir isotherm. The absolute surface coverage calculated from the IR absorbance saturates at 3.2 × 1014 cm-2. On the basis of this isotherm, the empirical rate constant ( ) that governs the rate-limiting step in 1-decene adsorption on HF-treated Si(100) is (3.3 ± 0.7) × 10-2 min-1. The thickness and cant angle of the decane monolayer at the saturation coverage are calculated from angle resolved X-ray photoelectron spectroscopy (AR-XPS). The calculated thickness ranges from 8.4 to 18 Å due to the uncertainty in the attenuation lengths of C(1s) and Si(2p) photoelectrons through the decane layer. For the same uncertainty, the calculated cant angle ranges from 0 to 55°. Spectroscopic ellipsometry is independently used to approximate the film thickness at 16 Å. Monitoring the decane monolayer over a period of 50 days using AR-XPS indicates that the Si surface underneath the decane monolayer gets oxidized with time, leading to the degradation of the decane layer.

Surface Modification of Corneal Contact Lens with Phosphoryl Choline by Glow Discharge

Polymers like poly(methylmethacrylate) (PMMA) and poly(2-hydroxyethylmethacrylate) (PHEMA) are widely used in the development of hard and soft contact lenses. Cell adhesion and deposition of chemicals such as calcium, lipoproteins and mucin on the lens surface cause visual acuity which is the main problem in extended uses of contact ocular lenses. In order to minimise the cell adhesion and other type of depositions, a method of surface modification of lens involving the use of phosphoryl choline, a phospholipid and the glow discharge technique has been described. The power variation of the lenses after modification has been checked using Topcon lensometer. The possible power changes of the modified samples due to the exposure to the normal light in the laboratory, darkness, ultraviolet (U.V.) light or saline have been investigated by taking the visible and ultra violet spectra using Beckman spectrophotometer. Surface energy variations after modifications of the samples have been checked by sessile drop water contact angle measurements. Glow discharge treatment increases the hydrophilicity of the samples. It seems, the modifications do not affect the power of hard contact lens significantly. It is also observed that the exposure of samples to the normal light in the laboratory, darkness, U.V. light or saline make no significant change in the visible and ultraviolet spectra of the samples before and after modification.