Photochemical functionalization of polymer surfaces for microfabricated devices

Herein we report the topochemical modification of polymer surfaces with perfluorinated aromatic azides. The aryl azides, which have quaternary amine or aldehyde functional groups, were linked to the surface of the polymer by UV irradiation. The polymer substrates used in this study were cyclic olefin copolymer and poly(methyl methacrylate). These substrates were characterized before and after modification using reflection-absorption infrared spectroscopy, sessile water contact angle measurements, and X-ray photoelectron spectroscopy. Analysis of the surface confirmed the presence of aromatic groups with aldehyde or quaternary amine functionality. Enzyme immobilization and patterning onto polymer surfaces were studied using confocal microscopy. Enzymatic digests of protein were carried out on modified probes manufactured from thermoplastic substrates, and the resulting peptide analysis was completed using matrix-assisted laser desorption/ionization mass spectrometry. The use of functionalized perfluorinated aromatic azides allows the surface chemistry of thermoplastics to be tailored for specific lab-on-a-chip applications.     

Alteration in the surface properties of direct-current discharge-treated tetrafluoroethylene-ethylene copolymer films

A change in the contact properties of the surface of a tetrafluoroethylene-ethylene copolymer film by treatment of its samples mounted on the cathode and anode in a dc discharge has been studied. It has been shown that the modification leads to a significant improvement in the contact properties of the films owing to the appearance of oxygen-containing polar groups on the polymer surface. The formation of such groups has been proved by X-ray photoelectron spectroscopy. The peel strength of both the untreated and modified films was measured by the T-peel test method.     

Orientation and confinement of cells on chemically patterned polystyrene surfaces

UV/ozone oxidation was combined with a photomasking technique to produce adjacent regions of different chemistry on polystyrene (PS) surfaces. The surface chemistry and topography were studied using AFM, XPS and contact angle measurements. The physicochemical patterns were visualised by the condensation of water vapour upon the surfaces and by the differential attachment of Chinese hamster ovarian (CHO) cells. The orientation of CHO cells on 55 and 125 microm wide oxidised PS strips were measured and found to be highly dependent on the width of the oxidised feature. CHO cells in relatively close proximity to a linear polar/non-polar border showed significant axial alignment along the border. CHO cells can also be confined to specific regions of the polymer surface. Cells attached to larger areas (75 microm x 75 microm) were found to have a smaller average cell size than cells attached to the smaller (56 microm x 56 microm) areas.     

Alteration in the surface properties of direct-current discharge-treated tetrafluoroethylene-vinylidene fluoride copolymer films

A change in the contact properties of the surface of tetrafluoroethylene-vinylidene fluoride copolymer films by a dc discharge treatment has been studied, depending on the treatment time and the discharge current. It has been shown that the treatment of the films at the anode and cathode leads to a significant decrease in the contact angle and an increase in the total surface energy and its polar term. The change in the contact properties of the plasma-modified films during storage and heating has been studied as well. The experiments have shown that the formation of polyconjugated structures and crosslinking of macromolecules take place in the film surface layer during long-term treatment at the anode (>60 s, 50 mA), processes that result in an acetone-insoluble layer. The composition and surface structure of the films have been examined by Fourier-transform IR spectroscopy and X-ray photoelectron spectroscopy. The formation of new oxygen-containing groups and double bonds on the polymer surface and crosslinking of macromolecules in the case of anode treatment have been revealed. It has been found experimentally that the discharge treatment increases the peel strength in the Scotch® 810/copolymer film system.     

UV curing behaviors and hydrophilic characteristics of UV curable waterborne hyperbranched aliphatic polyesters

A series of waterborne hyperbranched polyesters (WBHPs) endcapped with methacrylic and salt-like groups in different ratios have been investigated as UV curable resins. The kinetic studies of the drying step and UV curing were carried out by FT-IR measurements. The drying of the film of 100 μm thickness was completed in less than 6 hr at 70°C or within 10 hr at 50°C in an oven. The influence of different photoinitiators and their concentrations, extent of unsaturation and acid content of WBHP on final unsaturation conversion was studied. The surface free energy is a critical character, which affects the surface properties of a cured film. So one method based on the measurement of contact angle of a pure liquid on a solid surface was applied to determine the polar and dispersive components of the surface energy of UV cured films. The investigations of surface energy of WBHPs illustrated that those with more acid content and thus higher polar component are more sensitive to water, while those containing less acid content and thus lower polar term are less water sensitive. Moreover, the UV cured films of WBHPs and their blends with commercial waterborne resins (trade name EB 210, EB 2002, EB 11 and IRR 160) have acceptable pendulum hardness varying from 55 to 180 sec. Copyright © 2003 John Wiley & Sons, Ltd.     

Improvement of wettability and detergency of polymeric materials by excimer UV treatment

The 172 nm ultraviolet (UV) excimer light was exposed to polyethylene (PE), polypropylene, poly(ethylene terephthalate) and nylon 6 surfaces in ambient air. Changes in the contact angle and particle deposition in liquid due to UV treatment were investigated from the viewpoints of wettability and detergency. For all polymers, the wettability and the acid-base component of the surface free energy evaluated by the contact angle measurements increased remarkably by UV treatment of 1 min. From surface analyses of the polymer surfaces by X-ray photoelectron spectroscopy and atomic force microscopy, oxygen concentration was found to increase after UV treatment, whereas little topographical change was observed. The deposition of PE and nylon 12 particles onto the polymer surface was examined, in situ, in water, water/ethanol mixture, ethanol and n-heptane. Although the number of deposited particles was largely dependent on the kinds of the particle, the substrate and the liquid, a significant decrease in the deposition due to UV treatment was confirmed in any system.     

Role of additives in the water vapor transport through block co-poly(amide/ether) membranes: effects on surface and bulk polymer properties

In the last years there has been a growing industrial interest in modifying the performance of traditional polymers by using additives, working as modifiers for processing, rheological, transport, bonding, and pigmentation properties. This work was focused on the understanding of the relationships between chemical structure and water vapour transport through a polymer matrix modified by different additives regarding hydrophilicity and molecular structure. A screening of the changes in surface energies and bulk morphology, as a function of the chemical nature and weight percent modifier, allowed estimating the effects on the water vapour transport through polymer membranes. Static and dynamic contact angle measurements explained the difference in surface wettability and affinity to polar species such as water molecules. Modifiers having polar groups improved the surface hydrophilicity, enhancing the breathability of the membranes, while hydrophobic components such as aromatic structures led to a reduction of the water vapour mass uptake onto the membrane surface. On the other hand, thermal analyses showed a tendency of the polymer structure to reduce its own mobility with consequent slowdown of the diffusion through polymer matrix. Modification with large and bulky structures disrupted the polymer packing density, but simultaneously increased the stiffness of the polymer chains, inhibiting the penetrant migration. As a result, balancing the effects due to modifier polarity and bulky structure, it is possible to change the performance of a polymer in terms of transport, going from breathable membranes to barrier films.     

Changes in silicon elastomeric surface properties under stretching induced by three surface treatments

Poly(dimethylsiloxane) (PDMS) substrates are used in many applications where the substrates need to be elongated and various treatments are used to regulate their surface properties. In this article, we compare the effect of three of such treatments, namely, UV irradiation, water plasma, and plasma polymerization, both from a molecular and from a macroscopic point of view. We focus our attention in particular on the behavior of the treated surfaces under mechanical stretching. UV irradiation induces the substitution of methyl groups by hydroxyl and acid groups, water plasma leads to a silicate-like layer, and plasma polymerization causes the formation of an organic thin film with a major content of anhydride and acid groups. Stretching induces cracks on the surface both for silicate-like layers and for plasma polymer thin coatings. This is not the case for the UV irradiated PDMS substrates. We then analyzed the chemical composition of these cracks. In the case of water plasma, the cracks reveal native PDMS. In the case of plasma polymerization, the cracks reveal modified PDMS. The contact angles of plasma polymer and UV treated surfaces vary only very slightly under stretching, whereas large variations are observed for water plasma treatments. The small variation in the contact angle values observed on the plasma polymer thin film under stretching even when cracks appear on the surface are explained by the specific chemistry of the PDMS in the cracks. We find that it is very different from native PDMS and that its structure is somewhere between Si(O2) and Si(O3). This is, to our knowledge, the first study where different surface treatments of PDMS are compared for films under stretching.     

Surface modification of vinylidene fluoride-hexafluoropropylene copolymer films by direct-current discharge treatment

Changes in the contact properties of the surface of a vinylidene fluoride-hexafluoropropylene copolymer film by dc discharge treatment were studied. It was found that the modification considerably improved the contact properties of the films because of the appearance of oxygen-containing polar groups on the polymer surface. The formation of these groups was detected by X-ray photoelectron spectroscopy and Fourier-transform IR spectroscopy.     

Photochemical modification and patterning of polymer surfaces by surface adsorption of photoactive block copolymers

We report a simple photolithographic approach for the creation and micropatterning of chemical functionality on polymer surfaces by use of surface-active block copolymers that contain protected photoactive functional groups. The block copolymers self-assemble at the substrate-air interface to generate a surface that is initially hydrophobic with low surface tension but that can be rendered hydrophilic and functional by photodeprotection with UV radiation. The block copolymer employed, poly(styrene-b-tert butyl acrylate), segregates preferentially to the surface of a polystyrene substrate because of the low surface tension of the polyacrylate blocks. The strong adsorption of block copolymers causes a bilayer structure to form presenting a photoactive polyacrylate layer at the surface. In the example described, the tert-butyl ester groups on the polyacrylate blocks are deprotected by exposure to UV radiation in the presence of added photoacid generators to form surface carboxylic acid groups. Surface micropatterns of carboxylic acid groups are generated by UV exposure through a contact mask. The success of surface chemical modification and pattern formation is demonstrated by X-ray photoelectron spectroscopy and contact angle measurements along with imaging by optical and fluorescence microscopy methods. The resultant chemically patterned surfaces are then used to template patterns of various biomolecules by means of selective adsorption, covalent bonding and molecular recognition mechanisms. The surface modification/patterning concept can be applied to virtually any polymeric substrate because protected functional groups have intrinsically low surface tensions, rendering properly designed block copolymers surface active in almost all polymeric substrates.     

Solvatochromic azamethine dyes for probing the polarity of gold-cluster-functionalized silica particles

Azamethine dyes of the merocyanine type [4-(N,N-di-n-butylamino)-2-methylphenyl][2,4-di-keto-3-[N'-(n-hexyl)]-5-cyano-6-methyl-3-pyridinio]-1-azamethine (1) and [4-(N,N-diethylamino)-2-(N'-tert-butylcarboxy)-amidophenyl]-[2,4-diketo-3-[N"-(n-hexyl)]-5-cyano-6-methyl-3-pyridinio]-1-azamethine (2) have been used as surface-polarity indicators for gold-cluster-functionalized silica particles. Their UV/Vis absorption maxima range from about lambda=600 to 700 nm as a function of solvent polarity and are clearly separated from the surface plasmon UV/Vis absorption band of gold (lambda approximately 520-540 nm). Solvatochromism of both dyes has been investigated in 26 solvents of different polarity. The positive solvatochromic band shifts of 1 and 2 can be well expressed in terms of the empirical Kamlet-Taft solvent polarity parameters alpha and pi*. They are mainly sensitive to the dipolarity/polarizability (pi* term; 70-75 %) and HBD (hydrogen-bond donating) acidity (alpha term) of the solvent. Both dyes adsorb readily on functionalized silica samples from solutions in 1,2-dichloroethane or cyclohexane. The surface polarities of gold-cluster-functionalized silica particles, with and without co-adsorbed L-cysteine and poly(ethylenimine), have been investigated by using these solvatochromic dyes. The specific interaction of dye 2 with cysteine has been examined independently by quantum-chemical calculations by using the AM1 and PM3 methods.     

Facile Protection of Lithium Metal for All-Solid-State Batteries

A nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross-linkable silane groups with a layer of ally-ether-ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4 μm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li-metal/garnet contact.     

Surface energy of fluorinated surfaces

By fluorinating the surface of a polymer, the hydrogen bonding energy of a polar surface has been defined. The contact angles for three solvent classes; nonpolar, polar and hydrogen bonding, on a polar surface results in the separation of dispersion, polar, and hydrogen bonding energies. Both critical surface tension plots and theoretical calculations were used to define the surface energy for fluorinated polyethylene.     

Investigations on the Stability of Plasma Modified Silicone Surfaces

In this work it was investigated the effect of the exposure to different plasmas on the wettability of silicone samples. We have observed that oxygen. argon, and hydrogen glow discharges are quite effective in reducing the water contact angle of such polymer. However, indifferently to efficiency of the treatment, practically all the modified surfaces recovered great part of their original hydrophobicity. We have investigated this hydrophobic recovery using surface energy measurements and theoretical simulations based on the exponential decay of the population of polar groups on the surface. According to our results such recovery can be attributed to the decrease of polar species at the interface water–polymer surface.     

Polymer synthesis from 1-aminonaphthalene in direct-current discharge

Thin 1-aminonaphthalene polymer films have been obtained for the first time by polymerization at the cathode and anode in dc discharge. The elemental composition, chemical structure, and thermal stability of the polymer have been studied by pyrolysis chromatography, IR and UV spectroscopy, and thermogravimetry, respectively. The surface contact properties of the films and their thickness have been determined with a microinterferometer.     

UV‐Induced Tetrazole‐Thiol Reaction for Polymer Conjugation and Surface Functionalization

A UV‐induced 1,3‐dipolar nucleophilic addition of tetrazoles to thiols is described. Under UV irradiation the reaction proceeds rapidly at room temperature, with high yields, without a catalyst, and in both polar protic and aprotic solvents, including water. This UV‐induced tetrazole‐thiol reaction was successfully applied for the synthesis of small molecules, protein modification, and rapid and facile polymer–polymer conjugation. The reaction has also been demonstrated for the formation of micropatterns by site‐selective surface functionalization. Superhydrophobic–hydrophilic micropatterns were successfully created by sequential modifications of a tetrazole‐modified porous polymer surface with hydrophobic and hydrophilic thiols. A biotin‐functionalized surface could be fabricated in aqueous solutions under long‐wavelength UV irradiation.     

Photolabile carboxylic acid protected terpolymers for surface patterning. Part 1: Polymer synthesis and film characterization

We present the synthesis and characterization of a series of photolabile phenacyl derivative polymers and their subsequent thin film preparation. These systems are composed of up to three methacrylate units: a photolabile component including a p-methoxyphenacyl moiety which after selective irradiation (UV/laser) can provide free carboxylic groups in specific areas for further modification; an anchoring unit, trimethoxysiloxane or glycidyl methacrylate derivative, which allows the covalent attachment of the polymer to the substrate; and a spacer, methyl methacrylate or styrene, which in the appropriate proportion ensures the formation of films with good quality. Structural and thermal properties of these materials have been analyzed by means of NMR, FTIR, elemental analysis, UV, gel permeation chromatography, differental scanning calorimetry, and thermogravimetric analysis. The polymers have been subsequently processed by spin coating to render ultrathin films (<50 nm). Topographic and structural characterization studies of the films have been carried out with atomic force microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. The extent of the substrate attachment of the polymers depending on the nature of the anchoring groups have been studied by ellipsometry and FTIR.     

The Si-B chromophore: A joint experimental and theoretical investigation

Silylboranes with aromatic substituents linked to boron and silicon exhibit an unexpected absorption band in the UV-Vis spectral region. When polar groups were introduced, a marked solvatochromic effect was observed in their fluorescence emission spectra, revealing a strong excited state dipole moment. Semi-empirical MNDO/d and AM1 calculations showed that, upon UV excitation, the polarity of the Si-B bond increased and the aromatic π-electrons migrated toward the Si-B bond, consistent with experimental observations.     

Surface modification of LDPE film by CO2 pulsed laser irradiation

The influence of the pulsed CO₂ laser irradiation on the surface structure of the LDPE film was investigated. Significant changes were observed on the surface of laser treated films as it was verified by the attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy and contact angle-measurement. Formation of polar functional groups onto the LDPE surfaces exhibited by the ATR-FTIR spectra was shown to be strongly dependent on the number of the CO₂ laser pulses. The intensity of the polar groups increased with increasing the number of pulses up to two and then slightly decreased at three laser pulses. This was also confirmed with the contact angle measurements in which the sample subjected to two laser pulses showed the highest wettability i.e. the lowest water drop contact angle. The concentration of peroxide groups formed on the surface of the laser treated films was determined quantitatively by UV spectroscopic method using iodide procedure. The latter results showed a similar trend with the results obtained using FTIR spectroscopy.