Tailoring Silica Surface Properties by Plasma Polymerization for Elastomer Applications

The surface properties of reinforcing fillers are a crucial factor for dispersion and filler–polymer interaction in rubber compounds, as they strongly influence the final vulcanized properties of the rubber article. Silica is gaining more and more importance as reinforcing filler for rubbers, as it allows for a reduction of rolling resistance and thus energy losses in tires, compared to the use of carbon black as filler. However, silica and common elastomers differ greatly in polarity and, therefore, are difficult to mix and thus have little interaction. In the present study plasma-coating of silica-filler with acetylene, thiophene and pyrrole is applied, and the surface-treated silicas are blended with S-SBR rubber, in an attempt to enhance the compatibility between the two. The dispersion and reinforcing effects of the modified silicas are investigated and compared with untreated and silanized silica. The relative rankings of the various coatings in reduction of filler–filler interaction, improved dispersion, enhanced polymer–filler interaction, apparent crosslink density and tensile mechanical properties are mutually different. Where the best silica dispersion and largest reduction in filler–filler interaction are obtained with polyacetylene coating and the worst with polythiophene coating, but the tensile properties achieved with the polythiophene coating are far better than all others. Apparently, the sulfur contained in the thiophene-moiety enhances the filler–polymer interaction and contributes to the degree of crosslinking. Unmodified silica performs worst in all aspects, also because its acidic nature harms the preferably alkaline vulcanization process. Silane treatment of silica has a positive effect on reduction of filler–filler interaction and improved dispersion, but has little effect on polymer–filler interaction in the still unvulcanized state. Its tensile properties after vulcanization are comparable with polyacetylene- or polypyrrole-coated silica. This investigation shows that the compatibility and interaction of silica with a polymer can be controlled by tailoring the surface energy of the filler by coating with plasma polymers. An appropriate monomer for the plasma polymerization process allows to improve the cured rubber properties.     

A Theoretical Improved Adhesively Bonded Bi-material Beam Model for FRP–RC Hybrid Beams

In this paper we present an improved bi-material beam theory with adhesive interface, which has been applied to the study of the interfacial behavior in a concrete beam reinforced by an externally bonded fibre reinforced polymer (FRP) plate. The work explicitly considers the interfacial slip effect on the structural performance by including the effect of adherend shear deformations. This new method needs only one differential equation to determine both shear and normal interfacial stress whereas the others solutions in the literature need two differential equations. Compared with previously published analytical results, this one improves the accuracy of predicting the interfacial stresses and the solution is in a closed form. This research is helpful in the understanding of the mechanical behavior of the interface and design of FRP–reinforced concrete (RC) hybrid beams.     

The gap between the measured and calculated liquid–liquid interfacial tensions derived from contact angles

We present our new findings about the causes of discrepancies between the measured and calculated liquid-liquid interfacial tensions derived from contact angles. The calculated ones are based on either the equation developed by Fowkes or that by van Oss, Chaudhury and Good (VCG), while the measured ones are based on the sessile drop, weight-volume by Jańzuk et al. and the axisymmetric drop shape analysis (ADSA) by Kwok and Neumann. Indeed, there are deviations between the calculated and measured results. For an immiscible liquid-liquid or liquid-solid interface, we prefer to employ Harkins spreading model, which requires the interfacial tension to be constant. However, for the initially immiscible liquid-liquid pairs, we propose an adsorption model, and our model requires the interfacial tension to be varying and the surface tensions of bulk liquids at a distance from the interface to remain unchanged. Thus, the difference between the initial and final interfacial spreading coefficients (S_i) equals the equilibrium interfacial film pressure (π_i)_e. According to our findings, the calculated interfacial tension represents the initial value (γ₁₂)_o, which differs from the equilibrium value (γ₁₂)_e obtained experimentally after some time delay. This expected gap at a reasonable time frame is chiefly caused by the equilibrium interfacial film pressure between the two liquids. The initial (or calculated) interfacial tension can be positive or negative, while the equilibrium (or measured) one can reach zero. In fact, the former is shown to have more predictive value than the latter. A negative initial interfacial tension is described to favor miscibility or spontaneous emulsification but it tends to revert to zero instantaneously. Thus, a miscible liquid mixture should have zero interfacial tension. In response to recent papers by Kwok et al., we show that the disagreements between the calculated and measured interfacial tensions are definitely not caused by the failure of the VCG approach. Correct interfacial tensions are calculated for liquid pairs containing formamide or dimethyl sulfoxide (DMSO) by using the dispersion components cited in Fowkes et al.'s later publication. With the corrected surface tension components, the equilibrium interfacial film pressures (π_i)_e's for at least 34 initially immiscible liquid pairs have been calculated. These values are generally lower than the corresponding spreading pressures π_e's obtained by others using the Harkins model. Recently, we established a relationship between these two film pressures with the Laplace equation and found a new criterion for miscibility to be (π_i)_e = π_e.     

Enhanced interfacial adhesion of carbon fibers to vinyl ester resin using poly(arylene ether phosphine oxide) coatings as adhesion promoters

Poly(arylene ether phosphine oxide)s (PEPO) were prepared and utilized to coat carbon fibers to enhance the interfacial adhesion with vinyl ester resins. For comparison, poly(arylene ether sulfone) (PES), Udel^® P-1700, and Ultem^® 1000 were also used. The interfacial shear strength (IFSS) of thermoplastic polymer-coated fibers was measured via microbond pull-out tests. The interfacial adhesion between thermoplastics and as-received carbon fibers was also measured in order to investigate the adhesion mechanism. Thermoplastic polymer-coated fibers exhibited a higher IFSS than the as-received fibers with vinyl ester resin, and with thermoplastic polymers. PEPO-coated fibers showed the highest IFSS, followed by Udel^®, PES, and Ultem^®-coated fibers. The high IFSS obtained with PEPO coating could be attributed to the phosphine oxide moiety, which provided a strong interaction with functional groups in the vinyl ester resin and also on carbon fibers. A diffusion study revealed the formation of a clear interphase not only between PEPO and the vinyl ester resin, but also between Udel^® (PES or Ultem^®) and the vinyl ester resin, although the morphology of the two interphases differed greatly.     

Internal stresses and adhesion of thin silicon oxide coatings on poly(ethylene terephthalate)

The effect of internal stresses on the cohesion and adhesion of a thin silicon oxide (SiO_x) oxygen-barrier coating, evaporated on a poly(ethylene terephthalate) (PET) film substrate was studied. Internal stresses were generated during annealing in the temperature range for recrystallization of the PET,during calendering in a multilayer structure where two SiO_x /PET films were laminated together with a polypropylene film, and during long-term thermal aging below the glass transition temperature of the polymer. The cohesion of the coating and its adhesion to the polymer substrate were derived from fragmentation tests, in which the failure of the oxide coating was analyzed as a function of the applied stress during uniaxial tensile loading of the substrate. The intrinsic coating strength at critical length and the interfacial shear strength were found to be equal to 1350 MPa and 73 MPa, respectively. It was found that none of the thermal treatments investigated altered the interfacial interactions. Rather, these treatments induced shrinkage of the PET substrate, which increased the coating internal compressive stress and the SiO_x /PET interfacial shear strength. A linear relationship between the SiO_x /PET interfacial shear strength and the coating internal stress was determined from a stress transfer analysis. The coefficient of this linear relationship, equal to-1.34 · h _c/l _c, where h _c is coating thickness and l _c is the critical stress transfer length, reproduces the experimental data with good accuracy.     

Determination of the metal/die interfacial heat transfer coefficient and its application in evaluating the pressure distribution inside the casting during the high pressure die casting process

Abstract

High pressure die casting (HPDC) experiments were conducted on a 650 t cold chamber die casting machine to study the interfacial heat transfer behaviour between casting and die. A 'step shape' casting and two commercial alloys namely ADC12 and AM50 were used during the experiments. Temperature and pressure measurements were made inside the die and at the die surface. The metal/die interfacial heat transfer coefficient (IHTC) was successfully determined based on the measured temperature inside the die by solving the inverse heat transfer problem. The IHTC was then used as the boundary condition to determine the 3-D temperature field inside the casting. Based on the predicted temperature distribution, the pressure distribution inside the casting was evaluated by assuming that the transferred pressure from the plunger tip of the injection side to the casting is primarily influenced by the solid fraction of the casting. Reasonable agreement was found between the determined pressure values and the measured pressures at the die surface of the casting.     

Influence of Differently Structured Aluminium–Polypropylene Interfaces on Adhesion

Polar groups were introduced on polypropylene surfaces for increasing the surface energy and the peel strength to evaporated aluminium layers. Three kinds of plasma processes were used for introducing such functional groups to polyolefin surfaces: low-pressure radio-frequency (RF) O₂ plasma exposure, atmospheric-pressure dielectric-barrier discharge (DBD) treatment in air, and the deposition of allylamine plasma polymer. The amino groups of the allylamine plasma polymer were also used as anchoring points for chemical introduction of covalently bonded spacer molecules equipped with reactive endgroups. Thus, silanol endgroups of a covalently bonded spacer were able to interact with the evaporated metal layer. The Al–PP composites achieved a maximal peel strength of 470 N/m by exposing the polymer to the lowpressure O₂ plasma and 500 N/m on exposure to the atmospheric DBD plasma. After allylamine plasma polymerization and grafting of spacers, the peel strength was usually higher than 1500 N/m and the composites could not be peeled.     

A novel mathematical procedure to evaluate the effects of surface topography on the interfacial state of stress. Part II. Verification of the method for scarf interfaces

A mathematical procedure was developed to utilize the complementary energy method, by minimization, in order to obtain an approximate analytical solution to the 3D stress distributions in bonded interfaces of dissimilar materials. The stress solutions obtained predict the stress jumps at the interfaces, which cannot be captured by the current FEA methods. As a novel method, the penalty function is used to enforce the displacement boundary conditions at the interfaces. Furthermore, the mathematical procedure developed enables the integration of different interfacial topographies into the solution procedure. In order to incorporate the effects of surface topography, the interface is expressed as a general surface in Cartesian coordinates, i.e. F(x, y, z) = 0. In this paper, the scarf interface problem, i.e. y = x/2 surface is considered for verification of the method by comparison with finite element analysis (FEA) results. Comparison of the results reveals our new mathematical procedure to be a promising and efficient method for optimizing interface topographies.     

Surface characteristics and adhesion performance of black oxide coated copper substrates with epoxy resins

Black oxide is a conversion coating applied onto the copper substrate to improve its interfacial adhesion with polymeric adhesives. A comprehensive study is made to characterize the black oxide coating using various characterization techniques, including SEM, XPS, AFM, XRD, Auger electron spectroscopy, TEM, D-SIMS, RBS and contact angle measurements. It was found that the oxide coating consisted of cupric and cuprous oxide layers from the top surface to inside. The cuprous oxide layer was formed on the copper crystal surface, on which densely-packed fibrillar cupric oxide grew continuously until saturation. The cupric oxide had a fibrillar structure with high roughness at the nanoscopic scale, whereas the cuprous oxide was rather flat and granular. There was a continuous change in oxide composition with no distinct boundary between the two oxide layers. The bond strength between the epoxy resin and the oxide coated copper substrate increased rapidly at a low level of oxide thickness, and became saturated at thicknesses greater than about 800 nm. There were similar dependences of bond strength on surface roughness, oxide thickness especially of cupric oxide and surface energy, reflecting the importance of these surface characteristics in controlling the interfacial adhesion.     

Effects of XeCl excimer laser treatment of Vectran® fibers and their adhesion to epoxy resin

Vectran^® fibers, made using liquid crystalline polyester, were treated with pulsed XeCl excimer laser (308 nm) to alter their surface characteristics and, thus, improve their adhesion to epoxy resin. The treatments were carried out in air using varying numbers of pulses at different laser fluences. The effects of laser treatment on the fiber surface topography, chemistry and wettability have been investigated. Fiber/epoxy resin interfacial shear strength was measured using the microbead test. The surface roughness was characterized qualitatively and quantitatively using scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Changes in the surface energy were characterized using the Wilhelmy technique. Based on the SEM micrographs, the threshold fluence for the formation of surface structure was found to be less than 36 mJ/(pulse ? cm²). The laser treatments at fluences higher than the threshold fluence introduced periodic roll (wavy) structures on the fiber surface transverse to the fiber axis. From the AFM results, the fiber surface roughness was found to increase by up to 3.5 times the control fiber after the laser treatment. The dispersion component of the surface energy decreased, while the acid–base component of the surface energy increased significantly from 0 to 8.8 mJ/m² after the laser treatment. The Vectran^® fiber/epoxy resin IFSS increased by up to 75% after the laser treatment. This improvement is mainly attributed to higher surface roughness of the fiber.