The influence of structure of the interface and interphase on paint adhesion

It has been demonstrated earlier that significant adhesion enhancement to chemically inert polyolefins can be attained through surface grafted connector molecules reactive with oxidized substrate surface. The effectiveness of adhesion improvement through such tethered interfaces was shown to depend on the mode of interaction with the adjacent medium: interpenetration or chemical reaction, as well as surface density and length of grafted molecules. We have frequently observed that some systems, such as in painted products, fail through the delamination of the coating from the substrate surface at the stress levels well below the anticipated load-bearing capacity of the tethered interface. Two interim hypotheses have been formulated to explain the observed phenomenon: (i) The chain scission in surface oxidized polyolefins takes place not only in the uppermost polymer surface, but may propagate into the sub-surface region, thus creating a weak boundary layer which fails cohesively through its bulk, (ii) In order to increase the load-bearing capacity of the interphase, the sub-surface region of the substrate needs to be reinforced by short-chain molecules penetrating into and subsequently providing effective crosslinks between individual fragments of excessively oxidized and hence, weaker sub-surface part of the interphase. In this paper we verify the above hypotheses. The oxidized sub-surface layer reinforced by polyethyleneimine becomes an integral part of the effective interphase in addition to the tethered interface and the interpenetrated network of connector molecules and the paint.     

Using self-assembled monolayer technology to probe the mechanical response of the fiber interphase-matrix interphase interface

In this paper, a brief review of the fiber-matrix interphase/interface region is given for carbon- and glass-fiber composites. The substructure of the interphase/interface region is discussed in terms of three interphases: (a) the fiber interphase (FI), (b) the sizing interphase (SI), and (c) the matrix interphase (MI), and two interface regions: (a) the FI-SI interface and (b) the SI-MI interface. These substructures are a synthesis of the ideas advanced by Ishida and Koenig and Drzal. The schematic model of interphase deformation behavior originally given by Bascom is reconstructed to include research results from the above researchers. To systematically probe adhesion at the SI-MI interface, functionalized self-assembled monolayers (SAMs) using bonding and non-bonding C₁₁- type trichlorosilanes are prepared using the research of Menzel and Heise, and that of Cave and Kinloch as a guide. Results from this research are compared with short chain bonding and nonbonding silanes prepared by aqueous and non-aqueous deposition processes. The data were interpreted using the mechanisms proposed by Sharpe, Ishida and Koenig, and Drzal and the mathematical equation proposed by Nardin and Ward. For the non-bonding short-chain silane deposited by aqueous deposition, 90% of the adhesion was found to be due to mechanical interlocking, with the remaining adhesion due to physicochemical interactions. For the bonding short-chain silane deposited by aqueous deposition, the interface strength relative to the non-bonding short-chain silane increased by 31%. However the interfacial shear strength (IFSS) of this system was approximately 40% lower than the comparable bonding SAM interface. This difference was interpreted in terms of the propensity of the C₃-alkylamine to form cyclic ring structures in the MI region as described by Ishida, Koenig, et al. The SAM data also indicates that 70-85% of the maximum IFSS is obtained with 25-50% of the surface covered with functional groups. This suggests that steric hindrance, due to the size of the DGEBA molecules, restricts access to the functional groups on the surface. Therefore, only 35% of the surface functional groups are accessible for bonding in the DGEBA/m-PDA epoxy resin system.     

Thickness dependence of elastic modulus of polycarbonate interphase

The oligomer of bis-phenol A (oligo-PC) with M _w = 1300 and bis-phenol A polycar-bonate (PC) with M _w = 20 000 were deposited onto E-glass surface using SiCl₄ as the grafting and cross-linking agent. Thickness of the deposited layers was varied from 30 to 10⁶ nm and the layers were investigated as prepared and after thermal annealing at 245°C for 10 min in the air. Vibrational piezoelectric resonator technique and the speed of Rayleigh wave measurement were used to determine elastic moduli of the ultra thin layers deposited on flat E-glass substrate as a function of their thickness. In all cases, increase of the Young modulus of the interphase, E _i, with decreasing layer thickness, t _i, was observed. At a given thickness, the E _i of PC layer was significantly lower than that for the oligo-PC layer. Thermal annealing of the deposited PC layer resulted in a significant increase of its E _i compared to the as received layer. No significant change was observed for oligo-PC interphases. Increase of the shear strength of the interface, τ _a, with reducing interphase thickness, t _i, was observed. The observed increase of E _i with the decreasing t _i was ascribed to the reduction of the molecular mobility of chains near solid surface compared to their mobility in the bulk. Most probably, the observed increase of E _i after thermal annealing of PC was caused by rearrangement of both segment density distribution in individual PC coils near the solid surface and cooperative rearrangements of multiple PC chains. Since the oligomers attached to the surface attained presumably more regular extended conformations with lower conformation entropy compared to the PC random coils, the effect of thermal annealing was negligible. In agreement with theoretical predictions, increase of E _i at the same extent of interfacial interactions resulted in the observed increase of the τ _a measured using the single embedded fiber test.     

Interfacial region in blends of linear polymers formed in situ

Blends of linear polyurethane and poly(methyl methacrylate) were obtained by the simultaneous curing of the mixture of two monomers. It was shown that the blends obtained in situ are two-phase systems in which two phases enriched in one of the blend components are separated by an intermediate region, the interphase. From the DSC data the compositions of two phases were estimated. It was observed that introduction of a filler leads to the appearance of an additional temperature transition lying between glass transition temperatures of the two phases. The fraction of the interphase was calculated from the calorimetric data. The introduction of a filler increases this fraction. This may be considered as some improving of compatibility of the two components in the presence of a filler.     

Phase separation at the fiber–matrix interface in composites based on a thermoplastic/polyester blend

A study of the microstructure developing at the surface of glass fibers in a poly(vinyl acetate) (PVAc)/polyester blend is presented. Three different experimental methods are used: a technique based on the Wilhelmy method to measure the wettability of the fibers before curing, and both optical microscopy and atomic force microscopy in the pulsed-force mode to characterize potential phases splitting at the fiber–matrix interface after curing. It was found that, depending on the curing conditions and the concentration in PVAc, the surface treatment of the fiber could have a significant influence on the microstructure. For a concentration in PVAc lower than 5 wt% and a curing temperature of 80°C, extreme cases, such as the development of layers of one of the phases at the surface or the formation of lenses of one phase, were observed. In other cases, in particular for elevated temperatures and higher concentrations in PVAc, the fibers did not exert a significant influence on the morphology. It was also found that in such a reactive system, surface tension considerations alone are insufficient to explain the configuration of the phases at the surface of the fibers.     

Determination of the interface strength between two polymer materials by a new curved interface tensile test: Preliminary experimental results

Recently, the authors have proposed a new experimental method for the determination of adhesion strength between two different materials. A curved interface and special arrangement of materials is used for the tensile test of bimaterial specimens to avoid singular stress fields around corners and edges. The main advantage of the test consists in the fact that the strength is determined under conditions of a uniform tensile stress field normal to the interface in the region where debonding starts. The present paper presents experimental results for two bimaterial systems - PMMA/TPE and PC/TPE (two stiff standard polymers with a thermoplastic elastomer). The expected failure behaviour was observed during the experiments, thus enabling the estimation of adhesion strength by using calculated stress concentration factors. The influence of the radius of curvature is discussed in detail.     

Plasma-polymerized organosilicones as engineered interlayers in glass fiber/polyester composites

The plasma polymerization technique was used to surface modify glass fibers in order to form a strong but tough link between the glass fiber and the polyester matrix, and enable an efficient stress transfer from the polymer matrix to the fiber. Plasma polymer films of hexamethyldisiloxane, vinyltriethoxysilane, and tetravinylsilane in a mixture with oxygen gas were engineered as compatible interlayers for the glass fiber/polyester composite. The interlayers of controlled physico-chemical properties were tailored using the deposition conditions with regard to the elemental composition, chemical structure, and Young's modulus in order to improve adhesion bonding at the interlayer/glass and polyester/interlayer interfaces and tune the cross-linking of the plasma polymer. The optimized interlayer enabled a 6.5-fold increase of the short-beam strength compared to the untreated fibers. The short-beam strength of GF/polyester composite with the pp-TVS/O₂ interlayer was 32% higher than that with industrial sizing developed for fiber-reinforced composites with a polyester matrix.     

Effect of Geometry,Loading and Elastic Moduli on Critical Parameters in a Nanoindentation Test in Polymeric Matrix Composites with a Nonhomogeneous Interphase

Fiber nanoindentation models are developed for polymeric matrix composites with nonhomogeneous interphases. Using design of experiments, the effects of geometry, loading and material parameters on the critical parameters of the indentation test such as the load–displacement curve, the maximum interfacial shear and normal stresses are studied. The sensitivity analysis shows that the initial load–displacement curve is dependent only on the indenter type, and not on parameters such as fiber volume fraction, interphase type, thickness of interphase, and boundary conditions. The interfacial tensile radial stresses are not sensitive to indenter type, or to type and thickness of interphase, while the interfacial compressive radial stresses are sensitive mainly to boundary conditions and thickness of interphase; however, the influence of these factors on the interfacial radial stresses can be large. In contrast, the interfacial shear stress is sensitive to all factors, but the influence of the factors is relatively small.     

Finite element prediction of debonding onset in short fiber reinforced polymers incorporating a hybrid interphase region

A robust finite element procedure for investigating damage evolution in short fiber reinforced polymeric composites under external loads is developed. This procedure is based on an axisymmetric unit cell composed of a fiber, surrounding interphase and bulk matrix. The hybrid interphase concept involves a degraded material phase, the extent of which is material and property dependent. One of the most significant features of the model relies on establishment of variable adhesion conditions between the primary material phases. The unit cell is discretized into linearly elastic elements for the fiber and the matrix and interface elements which allow debonding in the fiber–matrix interface. The interface elements fail according to critical stress and critical energy release rate criteria. The tension and shear aspects of failure are uncoupled, although the resulting nonlinear problem is solved implicitly utilizing quasi-static incremental loading conditions. Final failure resulting from saturation and breakage is modeled by the vanishing interface element technique. Details of the propagation of interface cracks and the initiation of debonds are also observed and discussed for various shapes of fiber end. Numerical results reveal an intense effect of the fiber-end geometry on the initial fiber–matrix de-cohesion. The present finite element procedures can generate meaningful results in the analysis of fiber-reinforced composites.     

Numerical simulation of micro-scratch tests for coating/substrate composites

In this paper the micro-scratch test is simulated by ANSYS finite element code for thin hard coating on substrate composite material system. Coulomb friction between indenter and material surface is considered. The material elastic-plastic properties are taken into account. Contact elements are used to simulate the frictional contact between indenter and material surfaces, as well as the frictional contact after the detachment of coating/substrate interfaces has taken place. In the case of coating/substrate interfaces being perfectly bonded, the distributions of interfacial normal stress and shear stress are obtained for the material system subjected to normal and tangential loading. In the case of considering the detachment of interfaces, the length of interfacial detachment and the redistribution of stresses because of interfacial detachments are obtained. The influences of different frictional coefficients and different indenter moving distances on the distributions of stresses and displacements are studied. In the simulation, the interfacial adhesion shear strength is considered as a main adhesion parameter of coating/substrate interfaces. The critical normal loading from scratch tests are directly related to interfacial adhesion shear strengths. Using the critical normal loading known from experiments, the interfacial adhesion shear strength is obtained from the calculation. When the interfacial adhesion shear strength is known, the critical normal loading is obtained for different coating thicknesses. The numerical results are compared with the experimental values for composite materials of thin TiN coating on stainless steel substrate.     

Fibre matrix adhesion of natural fibres cotton,flax and hemp in polymeric matrices analyzed with the single fibre fragmentation test

In this research the adhesion and the resulting interfacial shear strength (IFFS) between the natural fibres flax, hemp and cotton and the polymer matrices polypropylene with coupling agent (MAPP) and polylactide acid (PLA) was surveyed with the single fibre fragmentation test (SFFT). The adhesion between MAPP and the fibres was good enough to produce fragments, whereas the adhesion between PLA and flax was too weak to transmit enough tension for fibre cracks which is clearly visible on SEM-photographs. Comparing the IFFS values of the fibres in MAPP with an equal fibre diameter shows that the IFFS value of flax is highest with 7.09 N/mm² followed by hemp 6.13 N/mm². The IFFS of cotton is a lot smaller (0.664 N/mm²). The critical fragmentation or fragmentation length of the bast fibres flax (3.16 mm) and hemp (3.20 mm) in MAPP is smaller than the critical fragmentation length of cotton (5.03 mm). The adhesion between the lignocellulosic fibres and MAPP is much better than between the lignin and pectin free cellulose fibre and MAPP. Possible reasons for this — the surface structure of the cotton fibre and its different chemical composition being made up of only cellulose, hemi-cellulose and wax with no pectin or lignin present — are discussed.     

A Fiber-Bundle Pull-out Test for Surface-Modified Glass Fibers in GF/Polyester Composite

The development of high-performance polymer composites is tightly bound with the functional surface modification of reinforcements. A new method, based on the principle of the fiber-bundle pull-out test, is proposed to analyze the interfacial properties between the long fibers in the form of a bundle and the polymer matrix. Specimen geometry and a test fixture were designed using finite element analysis. The method was verified for unsized and sized glass fibers embedded in polyester resin to demonstrate its applicability for a wide range of adhesion between fibers and the polymer matrix. The pull-out test can be used for a relative comparison of different surface modifications if the bundle geometry is unknown. The results of high reproducibility and sensitivity for interfacial properties make the method attractive.     

Influence of Grafting Density of Diblock Copolymers on Interfacial Assembly Behavior and Interfacial Shear Strength of Glass Fiber/Polystyrene Composites

To investigate the influence of the grafting density and the molecular structure of block copolymers on the interfacial assembly behavior and interfacial shear strength, macromolecular coupling agents, hydroxyl-terminated poly(n-butyl acrylate-b-styrene) (HO-P(BA-b-S)) were synthesized by atom transfer radical polymerization, and then chemically anchored on the glass fiber surfaces to form a well-defined monolayer. The phase separation and 'hemispherical' domain morphologies of diblock copolymer brushes at the polystyrene/glass fiber interface were observed. The interfacial assembly morphology differs with changes in the grafting density of diblock copolymers. When the grafting density is greatest, the highest height difference of the hemispherical domain and the largest surface roughness are achieved, as well as the best interface shear strength. It was also found that the copolymer brush with a PBA block of the polymerization degree (Xn) about 77 is the optimal option for the interfacial adhesion of PS/GF composites. Thus, the grafting density and molecular structure of diblock copolymers determines the interfacial assembly behavior of copolymer brushes, and therefore the interfacial shear strength.     

An AFM study of the effect of chemical treatments on the surface microstructure and adhesion properties of flax fibres

The mechanical properties of fibre-reinforced polymer composites are largely dependant on the adhesion between the matrix and the fibre. In order to enhance the interaction between flax fibres and unsaturated polyester resins, raw fibres were chemically modified using sodium hydroxide, sodium hydroxide plus acetic anhydride and formic acid-based treatments. The physical properties of the modified fibres were investigated by means of the atomic force microscopy. At first, the morphological analysis of the surfaces shows that after the chemical treatments, the fibres surface appear to be less heterogeneous in topology and smoother. Nonetheless, no significant roughness difference was found between the different treatments. Secondly, adhesion forces measurements were performed between a standard AFM silicon nitride tip and the fibres. The adhesion forces were found to vary according to the chemical treatment. The sodium hydroxide-based treatment was found to increase the adhesion force between the fibre and the AFM tip whereas the lowest adhesion force was found for the formic acid- based treated fibre. These results were attributed to the different hydrophilic character of the modified fibres. Due to the importance of the water layer adsorbed on the fibres, the adhesion forces between the AFM tip and the different samples are found to be mainly dominated by capillary forces in relation with the fibre's surface hydrophilicity.     

Adhesion strength study between plasma treated polyester fibres and a rubber matrix

In this work, the adhesion strength between poly(ethylene terephthalate) (PET) fibres and styrene-butadiene rubber (SBR) was studied. The effects of atmospheric plasma treatment, used to increase adhesion strength between PET fibres and the rubber matrix, were investigated and compared. It was confirmed that lubricants on the fibres caused a decrease in adhesion strength between the plasma treated reinforcing PET fibres and the SBR rubber matrix. These lubricants can be removed by acetone. When washed and treated in plasma, a substantial improvement in adhesion strength was observed. No ageing in air before combination with the rubber matrix was observed. This confirmed that the plasma streamers caused the creation of a new, relatively stable chemical species on the polymer surface. It suggests that the surface modification of PET fibres by plasma treatment at atmospheric gas pressure is a suitable and technologically applicable method for the improvement of adhesion strength of polyester reinforcing materials to rubber.     

Microstructure and oxidation behaviour of SiC fibre-reinforced Si3N4-AlN-Al2O3-Y2O3 matrix composites

A series of SiC fibre-reinforced Si₃N₄-AlN-Al₂O₃-Y₂O₃ matrix composites with different matrix compositions are fabricated by slurry infiltration followed by hot pressing at 1600°C for 30 min. The diffusion of yttrium and aluminium into fibres is apparent during the high temperature processing. All the as-processed composites show fracture with fibre pull-out. After heat treatment in air at 1000°C for 60 min, composites with minimal Y₂O₃ and Al₂O₃ in the matrix composition demonstrate the fracture behaviour with most extensive fibre pull-out. Composites with the highest aluminium and yttrium oxide content form an yttrium–aluminium–garnet phase and an aluminosilicate glassy phase. The latter phase provides an oxygen diffusion path, resulting in the removal of the carbon-rich interphase by oxidation. This results in catastrophic fracture without fibre pull-out after heat treatment of the composite in air.     

Enhancing the Fibre Matrix Adhesion of Natural Fibre Reinforced Polypropylene by Electron Radiation Analyzed with the Single Fibre Fragmentation Test

The effects of electron radiation on natural fibre reinforced polypropylene have been analyzed with the single fibre fragmentation test. Specimens of single hemp, flax, ramie and cotton fibres/fibre bundles embedded in a polypropylene sheet were irradiated with electron radiation of 10 MeV with intensities of 5, 15 and 33 kGy. The radiation led to a strain reduction of the polypropylene but did also improve the adhesion between polymer and flax, hemp and cotton fibres/fibre bundles. The critical fragmentation length and the interfacial shear strength (IFSS) of the composite specimens have been determined showing a clear increase of the IFSS of up to 50% compared to specimens with applied coupling agents. Due to the high strain reduction of the PP at intensities of 15 and 33 kGy the different fibres could only be compared at 5 kGy. The ramie fibre specimens could be analyzed at 5 and 15 kGy intensity showing higher IFSS values at the higher intensity. A possible explanation for the improvement is the forming of radicals with the cellulose chains of the natural fibres and the polypropylene molecules leading to crosslinking and, therefore, better adhesion between the different components.     

Anisotropic orientation of the carbon fiber/liquid crystalline epoxy resin composites

Anisotropic orientation of carbon fiber (CF)/liquid crystalline epoxy (LCE) resin composite was readily induced during curing on a CF surface along a long molecular axis of CF. Orientation of LCE was confirmed with polarized optical microscope (POM) and wide angle X-ray diffractometer (WAXD). In addition, anisotropic ordering of LCE was correlated with curing rate, dynamic mechanical properties and thermal expansion behaviors of CF/LCE composite. Curing of LCE was accelerated in the presence of CF and the rubbery modulus of the CF/LCE composites cured at low temperature was enhanced by long-range, long axis orientational ordering of the LCE resin along a CF surface. Fully cured CF/LCE composite showed a negative coefficient of thermal expansion in the fiber direction. These results obtained in this study are interpreted in terms of structural changes occurring during curing.