Decohesion Kinetics of PEDOT:PSS Conducting Polymer Films

The highly conductive polymer PEDOT:PSS is a widely used hole transport layer and transparent electrode in organic electronic devices. To date, the mechanical and fracture properties of this conductive polymer layer are not well understood. Notably, the decohesion rate of the PEDOT:PSS layer and its sensitivity to moist environments has not been reported, which is central in determining the lifetimes of organic electronic devices. Here, it is demonstrated that the decohesion rate is highly sensitive to the ambient moisture content, temperature, and mechanical stress. The kinetic mechanisms are elucidated using atomistic bond rupture models and the decohesion process is shown to be facilitated by a chemical reaction between water molecules from the environment and strained hydrogen bonds. Hydrogen bonds are the predominant bonding mechanism between individual PEDOT:PSS grains within the layer and cause a significant loss in cohesion when they are broken. Understanding the decohesion kinetics and mechanisms in these films is essential for the mechanical integrity of devices containing PEDOT:PSS layers and yields general guidelines for the design of more reliable organic electronic devices.     

Adhesion and Surface Interactions of a Self‐Healing Polymer with Multiple Hydrogen‐Bonding Groups

The surface properties and self‐adhesion mechanism of self‐healing poly(butyl acrylate) (PBA) copolymers containing comonomers with 2‐ureido‐4[1H]‐pyrimidinone quadruple hydrogen bonding groups (UPy) are investigated using a surface forces apparatus (SFA) coupled with a top‐view optical microscope. The surface energies of PBA–UPy4.0 and PBA–UPy7.2 (with mole percentages of UPy 4.0% and 7.2%, respectively) are estimated to be 45–56 mJ m^?2 under dry condition by contact angle measurements using a three probe liquid method and also by contact and adhesion mechanics tests, as compared to the reported literature value of 31–34 mJ m^?2 for PBA, an increase that is attributed to the strong UPy–UPy H‐bonding interactions. The adhesion strengths of PBA–UPy polymers depend on the UPy content, contact time, temperature and humidity level. Fractured PBA–UPy films can fully recover their self‐adhesion strength to 40, 81, and 100% in 10 s, 3 h, and 50 h, respectively, under almost zero external load. The fracture patterns (i.e., viscous fingers and highly “self‐organized” parallel stripe patterns) have implications for fabricating patterned surfaces in materials science and nanotechnology. These results provide new insights into the fundamental understanding of adhesive mechanisms of multiple hydrogen‐bonding polymers and development of novel self‐healing and stimuli‐responsive materials.     

Conductive Transparent TiNx/TiO2 Hybrid Films Deposited on Plastics in Air Using Atmospheric Plasma Processing

The successful deposition of conductive transparent TiN_x/TiO₂ hybrid films on both polycarbonate and silicon substrates from a titanium ethoxide precursor is demonstrated in air using atmospheric plasma processing equipped with a high‐temperature precursor delivery system. The hybrid film chemical composition, deposition rates, optical and electrical properties along with the adhesion energy to the polycarbonate substrate are investigated as a function of plasma power and plasma gas composition. The film is a hybrid of amorphous and crystalline rutile titanium oxide phases and amorphous titanium nitride that depend on the processing conditions. The visible transmittance increases from 71% to 83% with decreasing plasma power and increasing nitrogen content of the plasma gas. The film resistivity is in the range of ～8.5 × 10¹ to 2.4 × 10⁵ ohm cm. The adhesion energy to the polycarbonate substrate varies from ～1.2 to 8.5 J/m² with increasing plasma power and decreasing plasma gas nitrogen content. Finally, annealing the film or introducing hydrogen to the primary plasma gas significantly affects the composition and decreases thin‐film resistivity.     

Phototunable Underwater Oil Adhesion of Micro/Nanoscale Hierarchical‐Structured ZnO Mesh Films with Switchable Contact Mode

Controllable surface adhesion of solid substrates has aroused great interest both in air and underwater in solving many challenging interfacial science problems such as robust antifouling, oil‐repellent, and highly efficient oil/water separation materials. Recently, responsive surface adhesion, especially switchable adhesion, under external stimulus in air has been paid more and more attention in fundamental research and industrial applications. However, phototunable underwater oil adhesion is still a challenge. Here, an approach to realize phototunable underwater oil adhesion on aligned ZnO nanorod array‐coated films is reported, via a special switchable contact mode between an unstable liquid/gas/solid tri‐phase contact mode and stable liquid/liquid/solid tri‐phase contact mode. The photo‐induced wettability transition to water and air exists (or does not) in the micro/nanoscale hierarchical structure of the mesh films, playing important role in controlling the underwater oil adhesion behavior. This work is promising in the design of novel interfacial materials and functional devices for practical applications such as photo‐induced underwater oil manipulation and release, with loss‐free oil droplet transportation.     

Glyconectin Cell Adhesion Epitope, β-d-GlcpNAc3S-(1→3)-α-l-Fucp,Is Involved in Blastulation of Lytechinus pictus Sea Urchin Embryos

Glycans, as the most peripheral cell surface components, are the primary candidates to mediate the initial steps of cell recognition and adhesion via glycan–glycan binding. This molecular mechanism was quantitatively demonstrated by biochemical and biophysical measurements at the cellular and molecular level for the glyconectin 1 β-d-GlcpNAc3S-(1→3)-α-l-Fucp glycan structure (GN1). The use of adhesion blocking monoclonal antibody Block 2 that specifically recognize this epitope showed that, besides Porifera, human colon carcinoma also express this structure in the apical glycocalyx. Here we report that Block 2 selectively immune-precipitate a Mr 580 × 10³ (g580) acidic non-glycosaminoglycan glycan from the total protein-free glycans of Lytechinus pictus sea urchin hatched blastula embryos. Immuno-fluorescence confocal light microscopy and immunogold electron microscopy localized the GN1 structure in the apical lamina glycocalyx attachments of ectodermal cells microvilli, and in the Golgi complex. Biochemical and immune-chemical analyses showed that the g580 glycan is carrying about 200 copies of the GN1 epitope. This highly polyvalent g580 glycan is one of the major components of the glycocalyx structure, maximally expressed at hatched blastula and gastrula. The involvement of g580 GN1 epitope in hatched blastula cell adhesion was demonstrated by: (1) enhancement of cell aggregation by g580 and sponge g200 glycans, (2) inhibition of cell reaggregation by Block 2, (3) dissociation of microvilli from the apical lamina matrix by the loss of its gel-like structure resulting in a change of the blastula embryonal form and consequent inhibition of gastrulation at saturating concentration of Block 2, and (4) aggregation of beads coated with the immune-purified g580 protein-free glycan. These results, together with the previous atomic force microscopy measurements of GN1 binding strength, indicated that this highly polyvalent and calcium ion dependent glycan–glycan binding can provide the force of 40 nanonewtons per single ectodermal cell association of microvilli with the apical lamina, and conservation of glycocalyx gel-like structure. This force can hold the weight of 160,000 cells in sea water, thus it is sufficient to establish, maintain and preserve blastula form after hatching, and prior to the complete formation of further stabilizing basal lamina.     

Banana fiber/chemically functionalized polypropylene composites with in-situ fiber/matrix interfacial adhesion by Palsule process

Chemically functionalized maleic anhydride (MAH)-grafted polypropylene matrix has been used (in place of polypropylene as matrix with compatibilizer) to process banana fiber/chemically functionalized polypropylene (BF/CFPP) composites, without using any compatibilizer and without any fiber modification by Palsule process. Fiber/matrix interfacial adhesion generated, in-situ, due to interactions between BF and the MAH of the CFPP matrix has been established by Fourier transform infrared spectroscopy and scanning electron microscopy. Mechanical properties of the BF/CFPP composites developed by Palsule process with in-situ fiber/matrix interfacial adhesion in this study have been found to be higher than those of the matrix and it increases with increasing amounts of fibers in composites, and are better than properties of literature reported BF/polypropylene composites processed with compatibilizers. Measured modulus of BF/CFPP composites compares well with values predicted by rule of mixtures, Hrisch model, Halpin-Tsai equations and its modified Nielsen version, and with Palsule equation. The feasibility of developing natural fiber/MAH grafted polyolefin composites by Palsule process without using any compatibilizer and without any fiber treatment is demonstrated.     

Improving the adhesion between a aqueous PU and a polyamide fibre with silane

Glycidoxypropyltrimethoxysilane (GPS) and γ-aminopropyltrimethoxysilane (APS) were used to modify the surface chemistry of polyamide fibre. The surface chemistry was characterised using X-ray photoelectron spectroscopy. The silanol functional group was designed to be introduced on the surface of polyamide fibre to increase its chemical activity by N-alkylation of GPS and hydrolysis of APS, and to improve the poor interfacial adhesion between a polyamide 66 fibre and an aqueous polyurethane polymer adhesive. The microbond test was used to measure the interfacial shear strength between the waterborne PU adhesive and the polyamide fibre. It has been found that APS hydrolysis and GPS-alkylated fibre surface can be used to improve the interfacial adhesion of polyamide fibre to PU. The IFSS can be improved by N-alkylation of GPS from 5.0 to 8.4?MPa. After water immersion at 50?°C for 48?h, then drying, the IFSS increased to 8.8?MPa due to the plasticisation of PU in water. Better interfacial adhesion was also observed by the hydrolysis of APS, but not significantly improved by this method due to the relatively weak hydrogen bond at the interface between APS and polyamide fibre.     

Formation of adhesive phase onto high strength and modulus PE fiber by PE solution treatment for making PE fiber-reinforced PE composite

The method for the formation of adhesive phase onto polyethylene (PE) fiber surface by passage of the PE fiber through hot PE solutions has been investigated for making composite materials reinforced by the PE fibers. When the PE fiber is treated by the low density PE (LDPE) solution in o-xylene in the range of 120 to 135^°C, the tensile strength of the PE fiber is maintained at that of the original PE fiber. Adhesive strength between the PE fiber surface and LDPE phase formed on the PE fiber through the hot PE solution is found to be so high that the PE fiber itself is torn off. The application of the present method to PE fiber-reinforced PE composites will be expected.     

Fractal and structural aspects of adhesion in particulate-filled polymer composites

Two types of composites based on poly(hydroxy ether) and graphite with various amounts of a filler have been investigated by various methods. The methods have been used to estimate the characteristics of adhesion and interfacial layer, including its thickness and tensile strength and interdependence between these values and adhesion. The results are treated on the basis of the theory of irreversible aggregation, cluster theory of the polymer structure and fractal analysis. It is established that all important characteristics of adhesion, interfacial layer and mechanical properties are interconnected with the difference between fractal dimensions of the surface of the aggregates of filler particles and of a polymer matrix, whose structure is distorted under the influence of the filler surface.     

Interfacial interaction in carbon fiber/thermoplastic composites

This work was undertaken in order to increase the understanding of the mechanism responsible for fiber/matrix interaction in carbon fiber/thermoplastic composite. From results of previous study on carbon fiber/PEEK composite, which suggested that the formation of the fiber/ matrix interaction was primarily related to a chemisorption mechanism, a study was done of the conditions required to obtain efficient fiber/matrix interaction in PA-12 and PP/carbon fiber composites. The interest in studying carbon fiber composite based on PP and PA-12 was that these two matrices are very different in terms of reactivity, polyamide having many more reactive groups than polypropylene. As expected, due to the non-reactive chemical structure of the polypropylene, fiber/matrix interaction in carbon fiber/PP composite occurred only when the matrix was thermally degraded, i.e. when the composite was molded at high temperature or under long residence time at the melt temperature. For the carbon fiber/PA-12 composite, strong fiber/matrix interaction occurred readily at relatively low molding temperature, i.e. well before thermal degradation of the matrix. It was also found that the short beam shear strength in these composites seems to evolve with molding temperature, and a maximum interfacial strength was observed at a molding temperature corresponding to the thermal degradation of the matrix. This indicates that although matrix degradation often results in strong reduction in the composite performance, some matrix degradation can be beneficial in terms of interfacial mechanical properties. Finally, this work demonstrated that while the formation of fiber/matrix interaction seems to be primarily related to a chemisorption mechanism, the contribution of interphase crystallinity to the interfacial strength is not negligible. In fact, interfacial crystallinity was found to be essential to ensure optimum interfacial strength.