Underlying Polymer Layer Research Articles

Super-slippery silicone-based gel coating with a regenerative oil layer for long-term prevention of surface contamination

Polymer-based gel-type coatings, in which oil molecules are absorbed within polymer networks, have drawn attention as functional coatings to address fouling problems. However, surface drought caused by lubricant depletion limits the longevity of conventional gel-type coatings. In this study, a super-slippery long-chain entangled polydimethylsiloxane (LEP) gel that can self-regenerate a low-viscosity oil layer is proposed to enhance its long-term anti-fouling performance in both indoor and marine habitats. The proposed LEP gel coating can effectively prevent contamination from numerous liquids and protect aluminum surfaces from corrosion in seawater. Even when it was incubated with Porphyridium purpureum, marine red algae that readily stick to the surface, no biofilm was formed on the coated samples for 37 weeks. In field tests, no biological adhesion was observed on the coating surface which was applied to port structures and left for two summer months. This enhanced anti-contamination performance is mainly attributed to the dual protective barrier comprising the underlying polymer layer and regenerative oil layer. Due to special property of continuous self-regeneration of oil layer, the proposed LEP gel surface demonstrates much enhanced sustainability, compared to conventional gel-type coatings. Consequently, the long-term anti-contamination performance of the super-slippery LEP gel coating would pave the way for novel approach to its practical applications.

Guanidinium-Functionalized Polymer Dielectrics for Triboelectric Bacterial Detection.

Development of rapid detection strategies that target potentially pathogenic bacteria has gained increasing attention due to the increasing awareness for better health and safety. In this study, we evaluate an intrinsically antimicrobial polymer, 2Gdm, which is a poly(norbornene)-based functional polymer featuring guanidinium groups as side chains, for bacterial detection by the means of triboelectric nanogenerators (TENGs) and triboelectric nanosensors (TENSs). Attachment of bacteria to the sensing layer is anticipated to alter the overall triboelectric properties of the underlying polymer layer. The positively charged guanidinium functional groups can interact with the negatively charged phospholipid bilayer of bacteria and lead to bacterial death, which can then be detected by optical microscopy, X-ray photoelectron microscopy, and more advanced self-powered sensing techniques such as TENGs and TENSs. The double bonds present along the poly(norbornene) backbone allow for thermally induced cross-linking to obtain X-2Gdm and thus rendering materials remain stable in water. By monitoring the change in voltage output after immersion in various concentrations of Gram-negative Escherichia coli (E. coli) and Gram-positive Streptococcus pneumoniae (S. pneumoniae), we have demonstrated the utility of X-2Gdm as a new polymer dielectric for autonomous bacterial detection. As the bacterial concentration increases, the amount of adsorbed bacteria also increases, resulting in a decrease in the surface potential of the X-2Gdm thin film; this reduction in surface potential can cause a decrease in the triboelectric output for both TENGs and TENSs, which serves as a key working mechanism for facile bacterial detection. TENG and TENS systems are capable of detecting E. coli and S. pneumoniae within a range of 4 × 105 to 4 × 108 CFU/mL with a limit of detection of 106 CFU/mL. This report highlights the promising prospects of employing TENGs and TENSs as innovative sensing technologies for rapid bacterial detection by leveraging the electrostatic interactions between bacterial cell membranes and cationic groups present on polymer surfaces.

Influence of Catalytic Additives on the Formation of Nanostructured Carbon Layers on the Surface of Chlorinated Polyvinyl Chloride under a High-Power Ion Beam

The influence of catalytic additives (various organometallic and inorganometallic compounds) in chlorinated polyvinyl chloride on the formation of carbon nanofibers on its surface under a high-power ion beam of nanosecond duration is studied. Ferrocene, which provides the growth of long (up to 10 μm) nanofibers with a narrow diameter distribution and a small number of pores in the underlying polymer layer, seems to be the optimal catalyst for chlorinated polyvinyl chloride. We found that carbon nanofibers grow on the surface of chlorinated polyvinyl chloride containing zinc chloride as a catalytic additive. This fact indicates that there is a new mechanism for the growth of carbon nanofibers on the surface of chloropolymers under high-power radiation conditions.

Cellular Response to Non-contacting Nanoscale Sublayer: Cells Sense Several Nanometer Mechanical Property.

Cell adhesion is influenced not only from the surface property of materials but also from the mechanical properties of the nanometer sublayer just below the surface. In this study, we fabricated a well-defined diblock polymer brush composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-aminoethyl methacrylate (AEMA). The underlying layer of poly(MPC) is a highly viscous polymer, and the surface layer of poly(AEMA) is a cell-adhesive cationic polymer. The adhesion of L929 mouse fibroblasts was examined on the diblock polymer brush to see the effect of a non-contacting underlying polymer layer on the cell-adhesion behavior. Cells could sense the viscoelasticity of the underlying layers at the nanometer level, although the various fabricated diblock polymer brushes had the same surface property and the functional group. Thus, we found a new factor which could control cell spread at the nanometer level, and this insight would be important to design nanoscale biomaterials and interfaces.

Growth feature of PTFE coatings on rubber substrate by low-energy electron beam dispersion

Polytetrafluoroethylene (PTFE) coatings were prepared on Si and acrylonitrile-butadiene rubber substrates by low-energy electron beam dispersion. The effects of substrate nature, distance of target to substrate (dts) and coatings thickness on the surface morphology, structure, and tribological properties of the coatings were investigated. The results showed that substrate nature affects the shape and size distribution of surface conglomerations of PTFE coatings due to the interaction process of active dispersion particles with underlying polymer layer. Surface energy of PTFE coatings decreases first with the coatings thickness increases to 1.25 µm and then slowly increases with the thickness. Structure defects (pore, interstice, and so on) in the coatings increase with the thickness increases but reduce significantly with the dts increases. PTFE coating prepared at the dts of 20 cm had a higher intensity of the amorphous absorption bands. Friction experiment indicated that the destroyed area of the coatings in the friction region decreases with increases the coatings thickness but increases with the dts. The rubber modified by PTFE coatings with spherical structure possesses a higher stability in the friction process and a lower coefficient of friction. Copyright © 2015 John Wiley & Sons, Ltd.

Enhanced adhesion mechanisms between printed nano-silver electrodes and underlying polymer layers

We have characterized mechanisms to improve the adhesion between printed electrodes prepared from silver nanoparticle inks and underlying polymer layers. Adhesion strength was significantly improved by sintering the inks above the glass transition temperature of the polymer underlayers, whereby enhanced adhesion was realized through interfacial fusion between the silver electrode layer and the underlying polymer layer. The surface energy of the underlayer was found to be an important factor in the improvement of adhesive strength, in that larger and thicker interfused regions between layers were observed for underlayers that had higher surface energies.

Strain sensitivity and durability in p-type and n-type organic thin-film transistors with printed silver electrodes

Mechanical flexibility and compatibility of printing processes are key advantage that organic electronic devices have over conventional inorganic devices. However, one of the major remaining issues for organic devices is insufficient mechanical durability of printed electrodes. Here we have investigated the mechanical durability of both p-type and n-type organic thin-film transistors (TFTs) with ink-jet printed silver electrodes from silver nanoparticle inks. The modified silver nanoparticle inks enabled the strong adhesion to the underlying polymer layer, and the fabricated organic TFTs exhibited excellent reproducibility in the bending cycle tests. The strong channel length dependence on the strain sensitivity was observed in both p-type and n-type organic TFTs. The organic TFTs with a short-channel exhibited higher sensitivity to the bending strain. These results suggest that the flexible organic TFTs with printed silver electrodes have excellent mechanical durability and are useful for bending and strain sensors.

Direct Surface Force Measurements of Polyelectrolyte Multilayer Films Containing Nanocrystalline Cellulose

Polyelectrolyte multilayer films containing nanocrystalline cellulose (NCC) and poly(allylamine hydrochloride) (PAH) make up a new class of nanostructured composite with applications ranging from coatings to biomedical devices. Moreover, these materials are amenable to surface force studies using colloid-probe atomic force microscopy (CP-AFM). For electrostatically assembled films with either NCC or PAH as the outermost layer, surface morphology was investigated by AFM and wettability was examined by contact angle measurements. By varying the surrounding ionic strength and pH, the relative contributions from electrostatic, van der Waals, steric, and polymer bridging interactions were evaluated. The ionic cross-linking in these films rendered them stable under all solution conditions studied although swelling at low pH and high ionic strength was inferred. The underlying polymer layer in the multilayered film was found to dictate the dominant surface forces when polymer migration and chain extension were facilitated. The precontact normal forces between a silica probe and an NCC-capped multilayer film were monotonically repulsive at pH values where the material surfaces were similarly and fully charged. In contrast, at pH 3.5, the anionic surfaces were weakly charged but the underlying layer of cationic PAH was fully charged and attractive forces dominated due to polymer bridging from extended PAH chains. The interaction with an anionic carboxylic acid probe showed similar behavior to the silica probe; however, for a cationic amine probe with an anionic NCC-capped film, electrostatic double-layer attraction at low pH, and electrostatic double-layer repulsion at high pH, were observed. Finally, the effect of the capping layer was studied with an anionic probe, which indicated that NCC-capped films exhibited purely repulsive forces which were larger in magnitude than the combination of electrostatic double-layer attraction and steric repulsion, measured for PAH-capped films. Wherever possible, DLVO theory was used to fit the measured surface forces and apparent surface potentials and surface charge densities were calculated.

Selective growth and ordering of self-assembly on metal/polymer thin-film heterostructures via photothermal modulation

We show photothermal perturbation of morphology on planar aluminum/polymethyl methacrylate films, leading to alignment of location-specific self-assembled patterns. Local laser heating regularizes pattern formation in a selected area by inducing compressive stress in the metal layer as well as partial relaxation in the underlying polymer layer. Furthermore, this thermomechanical process enables the formation of complex structures such as line-gratings and concentric rings when an interferometric heating scheme is employed. Our photolithography-free technique achieves the spatial selectivity and controllability of growth initiation, providing a simpler way for bottom-up fabrication approach for integration of multicomponent devices.

Inkjet printing of light emitting quantum dots

We demonstrate the fabrication of diodes having inkjet printed light emitting quantum dots layer. Close packing of printed layer is shown to be influenced by surface morphology of the underlying polymer layer and size variance of quantum dots used. We extend our approach to printing quantum dots onto a quarter video graphics array substrate (76 800 monochrome pixels). The purity of emitted electroluminescent spectra of resulting devices is related to coverage integrity of printed layer, which in turn is shown to be affected by the number of printed drops per pixel.

Polymer through-hole membrane fabricated by nanoimprinting using metal molds with high aspect ratios

Polymer through-hole membranes were fabricated by nanoimprinting using metal molds with high aspect ratios, which were prepared by a replication process using an anodic porous alumina template. The introduction of a two-layer structure of polymers and the selective removal of underlying polymer layer allows the formation of polymer through-hole membranes. The obtained polymer through-hole membranes will be used for various applications that require highly ordered hole array structures with sufficient chemical stability.

Photochemical Attachment of Reactive Cross-Linked Polymer Films to Si/SiO2 Surfaces and Subsequent Polymer Brush Growth

Thin films consisting of a mixture of acrylate/methacrylate monomers were photochemically attached to modified silicon wafer surfaces. Reactive functionality was embedded into the photopolymer film by adding alkoxyamine monomers (inimers) that facilitate polymer brush growth in subsequent polymerization reactions. We present a careful examination of each of the steps, from substrate preparation to silane coupling agent coating, photopolymer attachment, and polymer brush growth. Several 3-methacryloxypropyl silanes were evaluated as silane coupling reagents. The surface roughness of wafers increased from 0.2 to 0.6 nm after treatment with silane. Curing of a thin photopolymer film did not increase the surface roughness. Interestingly, brushes of d8 polystyrene grown from the photopolymer surface displayed half the roughness of the underlying polymer layer, displaying a smoothing effect. All photopolymer films attached to the wafers utilizing a silane layer had excellent adhesion. We studied the film surfac...

Preparation and characterization of polymeric coatings with combined nitric oxide release and immobilized active heparin

A new dual acting polymeric coating is described that combines nitric oxide (NO) release with surface-bound active heparin, with the aim of mimicking the nonthrombogenic properties of the endothelial cell (EC) layer that lines the inner wall of healthy blood vessels. A trilayer membrane configuration is employed to create the proposed blood compatible coating. A given polymeric substrate (e.g., the outer surface of a catheter sleeve, etc.) is first coated with a dense polymer layer, followed by a plasticized poly(vinyl chloride) (PVC) or polyurethane (PU) layer doped with a lipophilic N-diazeniumdiolate as the NO donor species. Finally, an outer aminated polymer layer is applied. Porcine heparin is then covalently linked to the outer layer via formation of amide bonds. The surface-bound heparin is shown to possess anti-coagulant activity in the range of 4.80–6.39 mIU/cm 2 as determined by a chromogenic anti-Factor Xa assay. Further, the surface NO flux from the underlying polymer layer containing the diazeniumdiolate species can be controlled and maintained at various levels (from 0.5 to 60×10 –10 mol cm −2 min −1) for at least 24 h and up to 1 week (depending on the flux level desired) by changing the chemical/polymer composition of the NO release layer. The proposed polymeric coatings are capable of functioning by two complementary anti-thrombotic mechanisms, one based on the potent anti-platelet activity of NO, and the other the result of the ability of immobilized heparin to inhibit Factor Xa and thrombin (Factor IIa). Thus, the proposed polymeric coatings are expected to exhibit greatly enhanced thromboresistivity compared to polymers that utilize either immobilized heparin or NO release alone.

Molecular Depth Profiling of Multilayer Polymer Films Using Time-of-Flight Secondary Ion Mass Spectrometry

The low penetration depth and high sputter rates obtained using polyatomic primary ions have facilitated their use for the molecular depth profiling of some spin-cast polymer films by secondary ion mass spectrometry (SIMS). In this study, dual-beam time-of-flight (TOF) SIMS (sputter ion, 5 keV SF(5)(+); analysis ion, 10 keV Ar(+)) was used to depth profile spin-cast multilayers of poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), and trifluoroacetic anhydride-derivatized poly(2-hydroxyethyl methacrylate) (TFAA-PHEMA) on silicon substrates. Characteristic positive and negative secondary ions were monitored as a function of depth using SF(5)(+) primary ion doses necessary to sputter through the polymer layer and uncover the silicon substrate (>5 x10(14) ions/cm(2)). The sputter rates of the polymers in the multilayers were typically less than for corresponding single-layer films, and the order of the polymers in the multilayer affected the sputter rates of the polymers. Multilayer samples with PHEMA as the outermost layer resulted in lowered sputter rates for the underlying polymer layer due to increased ion-induced damage accumulation rates in PHEMA. Additionally, the presence of a PMMA or PHEMA overlayer significantly decreased the sputter rate of TFAA-PHEMA underlayers due to ion-induced damage accumulation in the overlayer. Typical interface widths between adjacent polymer layers were 10-15 nm for bilayer films and increased with depth to approximately 35 nm for the trilayer films. The increase in interface width and observations using optical microscopy showed the formation of sputter-induced surface roughness during the depth profiles of the trilayer polymer films. This study shows that polyatomic primary ions can be used for the molecular depth profiling of some multilayer polymer films and presents new opportunities for the analysis of thin organic films using TOF-SIMS.

A multilayer, high resolution, ion-bombardment-tolerant electron resist system

A multilayer, high resolution electron resist system, which withstands ion bombardment, has been developed. This system consists of four layers which are, from top to bottom: AZ1350B, a thin metal interlayer, PMMA, and a copolymer of PMMA. The bottom two layers define the actual pattern dimensions. Two independent developers have been chosen for these two layers in order to obtain controllably undercut resist profiles ideal for liftoff applications, while maintaining high resolution in the upper PMMA layer. The top two layers of the four-level system serve to provide a protective metal coating which prevents crosslinking of the underlying polymer layer. This allows processing involving ion bombardment, such as ion milling or reactive ion etching. Without this protective metal layer, difficulty is often encountered in liftoff processing after ion bombardment, due to the presence of a thin crosslinked polymer layer which resists solvent penetration. This resist system has been used in conjunction with reactive ion beam oxidation to fabricate high quality, small area, niobium–lead alloy tunnel junctions in an edge geometry. Using a standard Cambridge EBMF-2 microfabricator, junctions with linewidths as small as 0.25 μm have been produced. With the edge geometry, this corresponds to junction areas smaller than 4×10−10 cm2.