Polymer-Solid Interface Connectivity and Adhesion: Design of a Bio-Based Pressure Sensitive Adhesive

Adhesion at polymer-solid interfaces was explored for a new bio-based pressure sensitive adhesive (PSA) in terms of sticker groups, φ_X, on the polymer phase, receptor groups, φ_Y, on the solid surface, and the bond strength of the sticker-receptor X-Y acid-base interaction, χ. The polymer-solid interface restructuring models of Gong and Lee et al. were extended with new percolation models of entanglements and interface strength to determine the optimal sticker group concentration, φ?_X. For the general case where φ_Y and χ are constant, it is predicted that when φ_X < φ?_X, that the critical peel energy behaves as G_1c ～ φ_X/φ?_X and the locus of failure is adhesive between the polymer and the solid. However, when φ_X > φ?_X, failure occurs cohesively in a polymer-polymer interface adjacent to the solid and the strength decreases as G_1c ～ φ?_X/φ_X. The switch from adhesive to cohesive failure can be understood in terms of the changes in the chain conformations of the adhered chains and their decreasing interpenetration, X_i, with the bulk chains, via X_i ～ 1/r, where r = χφ_Xφ_Y. The optimal value of φ_X which maximizes the adhesion and determines the mode of failure is given by φ?_X ≈ 0.129/C_∝, and for typical values of the characteristic ratio C_∝ in the range 7–20, φ?_X ≈ 1% mole fraction, corresponding to about 2 sticker groups per entanglement molecular weight, M_e. This result was verified for a bio-based PSA synthesized from an acrylated high oleic fatty acid, which was copolymerized with maleic anhydride as the sticker group. The observed behavior is counterintuitive to the current wisdom for the effect of acid-based interactions on adhesion, where the strength is expected to increase with the number of X-Y contacts. The surprisingly low value of φ?_X ≈ 1% sticker groups which maximizes the adhesion strength can now be readily calculated using the percolation model of entanglements and fracture.     

Stick-Slip: Wet Versus Dry

A rubber lens (polydimethylsiloxane) is pressed against silanated or bare glass plates (Johnson-Kendall-Roberts (JKR) contact). As the plate slides with a velocity U, we measure the friction on the lens using a “macro Atomic Force Microscope (AFM)”, where the cantilever is a thin rectangular glass rod and the tip is the rubber lens. We observe the contact area via optical interferometry.

In air for “hard” lenses (Young's modulus E ≈ 1 MPa), we find smooth sliding on a model substrate, and a transition to stick-slip on a hysteretic substrate above a threshold velocity, V _M . For soft lenses (E ≈ 0.1 MPa), we observe Schallamach waves and stick-slip depending on normal force and the plate's velocity, U. When immersed in a liquid (silicone oils, water-glycerol mixtures), the contact remains dry at low velocities, but is invaded by a liquid film above a critical velocity, U _c . For hard lenses we observe smooth sliding and high friction below U _c , and low friction above U _c . For soft lenses, we find wet Schallamach waves for U < V _M and stick-slip instabilities at large velocities. In the stick-slip regime, the contact is wet in the slip phase, and dewets in the stick phase. We measure the period of the stick-slip cycle as a function of the liquid viscosity.

We interpret the stick-slip process by the formation and rupture of adhesive bonds (between the rubber polymer chains and active sites on the glass). Using a recent model, we can explain most of the data for the stick-slip period and slip threshold velocity.     

Effect of surface microstructure on the hydrophobicity of coatings

In this paper, coatings adopted SiO₂ nanoparticles ranging from 1 wt% to 7 wt% were in situ polymerized with low surface energy polymer, and different surface microstructures were built automatically during painting film. Copper microstructure surface was also achieved by chemical etching method and then was modified by low surface energy resin as contrast. The contact angle and the peel strength between the coating and bio-gooey simulacrum were studied. The results showed that the hydrophobicity of the coating was remarkably affected by the surface microstructure. The coating containing 5 wt% SiO₂ nanoparticles was covered with micro- and nano-scale salience and holes, and had the maximum contact angle and the minimum peel strength. Copper slices presented uniform micron and sub-micron structure surface when etching for 15 min and the contact angle reached a maximum of 125° after being modified.     

Arsenite removal from groundwater in a batch electrocoagulation process: Optimization through response surface methodology

In this study, influences of seven process variables such as initial pH (pH_i), applied current (i), operating time (t_EC), initial As(III) concentration (C_o), diameter of Fe ball anode (d_p), column height in the electrocoagulation (EC) reactor (h) and airflow rate (Q_air) for removal of As(III) from groundwater by a new air-fed fixed-bed EC reactor were evaluated with a response surface methodology (RSM). The proposed quadratic model fitted very well with the experimental data for the responses. The removal efficiencies and operating costs were determined to be 99% and 0.01 $/m³ at the optimum operating conditions (a pH_i of 8.5, 0.05 A, 4.94 min, d_p of 9.24 mm, h of 7.49 cm, Q_air of 9.98 L/min for 50 µg/L). This study clearly showed that the RSM in the EC process was a very suitable method to optimize the operating conditions at the target value of effluent As(III) concentration (10 µg/L) while keeping the operating cost to minimal and maximize the removal efficiency.     

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.     

Comparison of methanol/hydrochloric,ferric chloride acid versus tribochemical silica coating for adhesion of resin cement to zirconium dioxide

This study compared air-abrasion and etching regimens on adhesion of resin luting agent to zirconium dioxide. Ceramic specimens (LAVA, 3 M ESPE) (N = 16) were embedded in acrylic resin and exposed surfaces were polished. The specimens were randomly assigned into four groups (n = 12, 3 specimens for each disc): SC: Air-borne particle abrasion (30 μm aluminum oxide particles coated with silica, CoJet, 3 M ESPE); MH: Heated chemical solution (Methanol-800 mL; 37% Hydrochloric Acid-200 mL; Ferric Chloride-2 g) at 100 °C for 30 min, MHP: Primer (Metal/Zirconia Primer, Ivoclar Vivadent) + MH, P: Primer only (Metal/Zirconia Primer). Cylindrical molds (internal diameter: 0.7 mm; height: 1.5 mm) were placed on each conditioned specimen, filled with resin cement (Multilink Automix) and photo-polymerized for 60 s. After 24 h, the molds were removed and the specimens were stored in distilled water at 37 °C for six months). Microshear test was performed in a Universal Testing Machine (1 mm/min). Failures types were classified as adhesive, mixed, or cohesive. In another set of specimens (n = 2 per group) contact angle measurements were recorded. Data were analyzed statistically using Kruskal–Wallis and Dunn’s tests (α = 0.05). The surface conditioning method significantly affected the mean bond strength (MPa) (p < 0.0001): SC(18.3 ± 0.3)^a < P(5.00 ± 0.07)^b < MHP(4.7 ± 0.08)^c < MH(0.84 ± 0.01)^c. While Group SC showed mainly adhesive (58%) and mixed (41.7%) failure types, groups MH, MHP, and P presented exclusively adhesive failures. SC, MHP, and P (29–32°) showed lower contact angle than MH (78.9°). Volume loss was the highest with MHP (9.92 μl) followed by SC (9.67 μl).     

Study on poly (ethylene-co-vinyl acetate), acrylonitrile butadiene copolymer,and their blend reinforced with carbon black using position annihilation lifetime spectroscopy

Positron annihilation lifetime spectroscopy (PALS) have been used to investigate the effect of filling each of poly (ethylene-co-vinyl acetate) (EVA), acrylonitrile butadiene rubber (NBR), and their blend (50/50wt-%) with different concentrations of high-abrasion furnace (HAF) (0–60?phr). PALS is characterised by the free-volume parameters (V_h and F %), which is a measure of the size and fraction of free-volume holes in the composites. The results show that the variation in V_h and F % of free-volume holes depends on the chemical structure and the degree of crystallinity of each polymer. The NBR has a smaller size (127.78?ų) and lower fraction (4.18%) of free-volume holes than the corresponding free-volume holes (177.48?ų and 7.03%) in EVA. The size of the free-volume holes increases in EVA with increasing HAF content up to 20 phr in polymer matrix while it decreases in NBR. The fractions (F %) of free-volume holes decrease due to the reduction in positronium formation in polymer and positron trapping at polymer interface. The results also show an inverse correlation between free-volume parameters (V_h and F %) and tensile strength value, and a direct correlation with elongation at break as a function of HAF content in EVA and NBR. The electrical properties are negatively correlated with lifetime of free positron, τ₂, and positively with its relative intensity (I₂).     

The Effect of Zeolite Fixed Bed Depth on Lead Removal from Aqueous Solutions

Abstract

The effect of zeolite bed depth on lead removal from aqueous solutions by the column method has been examined. The results indicate that the increase of bed depth delays the breakthrough point and exhaustion point, and increases the contact time of the zeolite – lead solution, and the height of the mass transfer zone, h_z. The increase of the bed depth lowers the effect of axial dispersion on the mass transfer process. In order to predict the time necessary for exceeding the defined effluent concentration for a constant bed depth, the bed depth service time (BDST) approach has been used. Experimentally obtained breakthrough curves for the flow rate of 1 ml/min were used to derive the BDST approach equations. These equations were successfully used for modelling of the system for flow rates of 2 and 3 ml/min. The BDST equations have yielded modelled linear equations used for calculation of h_z. The increase of the flow rate increases h_z, which indicates that the zeolite–solution contact time is not sufficient. This may be attributed to the affect of axial dispersion on mass transfer on the solid-liquid interface.     

Analysis of structural,morphological alterations,wettability characteristics and adhesion to enamel after various surface conditioning methods

Minimal invasive dental reconstructions and orthodontic appliances are bonded to enamel without removing the enamel with rotating instruments but the top layer of enamel may be partially aprismatic and impair adhesion. The objectives of this study were to investigate the effect of mechanical surface conditioning methods for removing enamel on its structural, morphological alterations, wettability characteristics, and adhesion of resin-based cement to the conditioned surfaces. Maxillary human incisors (N = 40, n_quadrant = 160) were obtained and coronal sections were embedded in acrylic with their labial surfaces exposed. The teeth were randomly divided into four groups and the enamel surface of each tooth was divided into four quadrants. The surfaces were conditioned in a clockwise manner by one of the following methods: (1) Non-conditioned enamel acted as the control group (C); (2) Silicone-coated disk (Sof-Lex disc, Black, 3 M ESPE) (SD); (3) Diamond bur at slow speed (DB) and (4) Airborne particle abrasion (50 μm Al₂O₃, 2 bar, 5 s) (AA). Surface roughness was measured at each quadrant using a non-contact digital profilometer and contact angle measurements were performed using a goniometer. Enamel surfaces were then etched with 37% H₃PO₄ for 60 s and roughness and wettability measurements were repeated. The enamel surfaces in each quadrant received resin composite luting cement (Variolink II, Ivoclar Vivadent) incrementally in a polyethylene mold (diameter: 1 mm²; height: 4 mm) and photopolymerized. The specimens were stored in distilled water for 24 h at 37 °C until the testing procedures and then shear force was applied to the adhesive interface until failure occurred in a Universal Testing Machine (0.5 mm/min). Microshear bond (μSBS) was calculated by dividing the maximum load (N) by the bonding surface area of the resin cement. Representative enamel surfaces were analyzed under the scanning electron microscope (SEM) (x5000) to assess the surface morphology. Failure types were analyzed using optical microscope and SEM. Data (MPa) were analyzed using one-way ANOVA and Tukey`s test for each parameter and Linear model for group comparisons (α = 0.05). Surface conditioning method significantly affected the adhesion results (p < 0.001), surface roughness (p = 0.017), and contact angle (p < 0.001). Interaction terms were significant (p > 0.05). AA (338 ± 182) created significantly higher surface roughness compared to SD (308 ± 180) and DB (242 ± 197) (p < 0.05). After etching with 37% H₃PO₄, DB (307 ± 223) resulted in significantly lower roughness than those of SD (385 ± 173) and AA (414 ± 193) (p < 0.05). AA (40 ± 11) delivered significantly lower contact angle compared to those of SD (61 ± 9) and DB (59 ± 10). After etching with 37% H₃PO₄, AA (42 ± 10) and DB (50 ± 10) presented the lowest contact angle (p < 0.05). Mean μSBS results (MPa) showed significant difference between the experimental groups (p = 0.011) and were in descending order as follows: DB (20 ± 8)^a?a b < C (12 ± 5)^b. Failure types were predominantly mixed failure type between the enamel and the resin cement with more than half of the resin remained on the enamel surface (32 to 33 out of 40) in all groups. Cohesive failure in the enamel was not observed in any of the groups. SEM analysis showed that AA group leaves abundant particles on the enamel surface and after DB and AA, etching could not remove the particles completely and expose the enamel prisms.     

Capillary Flow of Power-Law Non-Newtonian Liquids in Circular Tubes

The penetration rate of power-law non-Newtonian liquids in a circular tube driven by the capillary pressure is derived. The dimensionless fractional height of liquid in the tube relative to the equilibrium height, χ = h(t)/h(∞), is calculated as a function of an appropriately chosen dimensionless time, permitting expression of the height-time dependence as a function of the reciprocal of the exponent in the power-law model, s = 1/n. It is found that the rate of penetration and, therefore, also withdrawal of liquid is dramatically retarded as the liquid becomes more strongly shear-thinning, i.e., as n becomes small relative to unity.     

Modulation of Adhesion at Silicone Elastomer–Acrylic Adhesive Interface

To characterize the role of small silica like nanoparticles (MQ resins) in the modulation of adhesion at polydimethyl siloxane (PDMS) elastomers–acrylic adhesive contacts, we have designed systems in which the roles of MQ resins in enhancing interactions at the interface and in increasing viscoelastic dissipations in the elastomer layer could be separated. First, the contact between elastomers with various MQ resin contents and PDMS layers made of densely grafted short chains has been investigated through Johnson–kendall–Roberts (JKR) tests, in order to characterize how the dissipations in the elastomer depend on the resin content. The same elastomers in contact with thin-surface-anchored acrylic layers were then tested through JKR tests to determine the role of enhanced interactions in the modulation of adhesion at the interface due to the resins. In these experiments, the thickness of the acrylic layer was kept small enough so that dissipations in the acrylic adhesive could be neglected. Both G ₀, the adhesive strength at zero fracture velocity, and G ( V), the velocity-dependent fracture toughness, strongly depend on the MQ resin content and on the contact time, suggesting the progressive building of strong interactions between acrylic and elastomer chains.     

Soft and Hard Adhesion

The force needed to pull a cylindrical stud from a soft elastomeric film depends on their elastic and geometric properties. For a rigid stud and a thick elastomeric film, the pull-off stress (σ) depends on the elastic modulus (E) of the film and the radius (a) of the stud as σ ～ (E/a)^1/2 (soft adhesion). However, when the film is very thin, the pull-off stress is significantly higher than the case with thick films, and its value depends on the elastic modulus and the thickness (h) of the film as σ ～ (E/h)^1/2 (hard adhesion). Here, we study the pull-off behavior of a soft cylindrical stud, one flat end of which is coated with a high modulus thin baseplate. As the flexural rigidity of this baseplate is varied, we observe the transition between the two types of adhesion. We present a simple physical interpretation of the problem, which could be of value in understanding various biofouling and adhesive situations.     

A.C. Conductivity and Dielectric Properties of Polycarbonate Sheet

ABSTRACT

The a.c. conductivity σ_a.c(ω), the dielectric constant ?′ and dielectric loss ?″ of polycarbonate sheet have been studied in the frequency range 1.5 × 10²–5 × 10⁶ Hz and temperature range 294–473 K. A.c. conductivity σ_a.c(ω) results show that it depends strongly on the frequency and slightly on the temperature, with activation energy between 0.0003 and 0.085 e.V. The a.c. conductivity σ_a.c(ω) as a function of frequency is well described by a power law Aω^S where S is the frequency exponent. The obtained values of S < 1 in the first region over the frequency range 1.5 × 10²–4 × 10³ Hz, the temperature dependence of both a.c. conductivity σ_a.c(ω) and the parameter S are reasonably well interpreted by the correlated barrier hopping (CBH) model. The second region, where S > 1 over the frequency range 4 × 10³–5 × 10⁶ Hz, has a strong dependence on the frequency but near independence of the temperature, suggesting that the conductivity may be interpreted by the Maxwell–Wagner (M–W) dispersion. In the first region, the optical band gap of the material, E_g, and the maximum barrier height, W_m, are calculated, suggesting that there is agreement with that proposed by the theory of hopping of charge carriers over potential barrier as suggested. Spatial inhomogeneity may affect the conduction mechanisms in polycarbonate. The experimental values of dielectric constant, ?′ and dielectric loss, ?″, show their dependence on temperature and frequency.     

Effect of surface heat transfer coefficient gradient on thermal shock failure of ceramic materials under rapid cooling condition

A rapid thermal processor (RTP) device as well as quenching technique is employed to systematically investigate the effect of surface heat transfer coefficient (h) gradient on thermal shock failure of a hot-pressed ZrB₂-based ceramic. Two typical kinds of quenchant with different surface h gradients during quenching tests, water and boiling water, are used for this study. When water as the cooling medium, two different cooling modes of indirect contact cooling by RTP device and direct contact cooling by quenching are also studied. The experimental results and related numerical simulations illustrate that surface h gradient plays an important role in thermal shock failure. This study confirms the previous presumption that the combination of body temperature gradient and surface h gradient leads to thermal stress damage and thermal shock failure. Under water quenching condition, water phase changes form bubbles randomly and produce great surface h gradient. Accordingly, critical body temperature gradient (V(max)_c) is small (~ 270?°C?s^?1). Under aqueous polymer quenching condition, the introduction of polymer chains into water lowers the random formation of steam bubble and mediates the surface h gradient. The corresponding V(max)_c hence become larger (~ 500?°C?s^?1). Under boiling water quenching condition, there is no surface h gradient and V(max)_c is even larger (> 600?°C?s^?1). This study provides useful complementary information for understanding the thermal shock behavior and gives suggests for predicting materials performance in actual service.     

Densification and mechanical properties of boron carbide prepared via spark plasma sintering with cubic boron nitride as an additive

Hexagonal boron nitride (h-BN) can reinforce boron carbide (B₄C) ceramics, but homogeneous dispersion of h-BN is difficult to achieve using conventional methods. Herein, B₄C/h-BN composites were manufactured via the transformation of cubic (c-) BN during spark plasma sintering at 1800 °C. The effects of the c-BN content on the microstructure, densification, and mechanical properties of B₄C/h-BN composites were evaluated. In situ synthesized h-BN platelets were homogeneously dispersed in the B₄C matrix and the growth of B₄C grains was effectively suppressed. Moreover, the c-BN to h-BN phase transformation improved the sinterability of B₄C. The sample with 5 vol.% c-BN exhibited excellent integrated mechanical properties (hardness of 30.5 GPa, bending strength of 470 MPa, and fracture toughness of 3.84 MPa⋅ m^1/2). Higher c-BN contents did not significantly affect the bending strength and fracture toughness but clearly decreased the hardness. The main toughening mechanisms were crack deflection, crack bridging, and pulling out of h-BN.     

Delamination Mechanics of a Clamped Rectangular Membrane in the Presence of Long-Range Intersurface Forces: Transition from JKR to DMT Limits

A 1-dimensional rectangular freestanding membrane clamped at opposite ends adheres to the planar surface of a rectangular punch. A tensile load applied to the punch causes the membrane to deform and gradually delaminate from the substrate. At equilibrium, the applied load is balanced by the disjoining pressure at the membrane-punch interface with range, y, and magnitude, p. Applying the Dugdale-Barenblatt-Maugis cohesive zone approximation, the disjoining pressure is taken to be uniform and confined to a finite cohesive length at the contact edge. For a fixed adhesion energy, γ = p y, we investigate the following: (i) the Derjaguin-Muller-Toporov (DMT) limit where y → ∞ and p → 0, (ii) the Johnson-Kendall-Roberts (JKR) limit where y → 0 and p → ∞, and (iii) the general case for intermediate but finite y and p. Delamination continues until the contact area shrinks to a line prior to “pinch-off”. The results are compared with the 2-dimensional axisymmetric membrane counterpart.     

Evaporation of Ethanol-Water Mixture Drop on Horizontal Substrate

This study investigates the evaporation of sessile drop comprising ethanol and water mixture on horizontal poly methyl methacrylate surface. The contact angle (θ) and contact radius (R) of ethanol-water mixture drop are recorded with time, considering the impacts of presence of ethanol. With excess ethanol, the drop evaporation is principally controlled by a phase in which both the contact angle and contact radius are falling. A diffusional model assuming linear relation between contact radius and time is proposed as θ = eR ^?3 + cR ^?1, where e and c denote fitting coefficients. This model correlates with the experimental data.     

Could readily silanized silica particles substitute silica coating and silanization in conditioning zirconium dioxide for resin adhesion?

This study investigated the effect of particle types with different morphology and surface properties on the wettability and adhesion of resin cement to zirconia. Zirconia specimens (5 × 5 × 1 mm³) were wet polished. Specimens were randomly assigned to one of the following protocols (N = 36, n = 9 per group): Group CON: Control, no surface conditioning; Group AL: Chairside air-abrasion with aluminium trioxide (50 μm Al₂O₃) + silane; Group SIL: Chairside air-abrasion with alumina particles coated with silica (SIL) (30 μm SiO2, SilJet) + air-drying + silane; Group 4: Chairside air-abrasion with readily silanized silica particles (SILP) (30 μm SiO_2, SilJet Plus). Adhesive resin was applied and resin cement (Variolink II, Ivoclar) was bonded using polyethylene moulds and photo-polymerized and aged (thermocycling, 6.000 cycles, 5–55 °C). Shear bond test was performed using Universal Testing Machine (1 mm/min). Pretest failures were considered 0 MPa. Contact angle measurements were performed (n = 2/group, sessile drop with water). Data (MPa) were analyzed (ANOVA, Tukey’s (α = 0.05). Two-parameter Weibull distribution values including the Weibull modulus, scale (m) and shape (0), values were calculated. Contact angle measurements were in descending order as follows: SIL (74°)^c < CON (60°)^c < AL (51°)^b < SILP (40°)^a. Bond strength (MPa) with SIL (17.2 ± 4)^a and SILP (17.3 ± 1.9)^a demonstrated no significant difference (p > 0.05), being higher than AL (8.4 ± 1.5)^b and CON (0)^c (p < 0.05). Failure types were exclusively adhesive in all groups. Weibull distribution presented the highest shape (0) for SILP (10.8). SILP presented better wettability than AL. SILP provided similar bond strength to SIL. Readily silanized silica particles may substitute for conventional silica coating and silanization.     

Plasma and Silane Surface Modification of SiC/Si: Adhesion and Durability for the Epoxy–SiC System

Gaseous plasma pretreatments and surface derivatization using silane coupling agents (SCA) have been used to enhance the adhesive bonding of an epoxy to SiC-coated Si wafers (SiC/Si). The surface modification approaches included 1) an SCA treatment using 3-aminopropyltriethoxysilane (APS) or 3-glycidoxypropyltrimethoxysilane (GPS) and 2) an oxygen plasma pretreatment followed by a silane treatment. Durability was evaluated by immersing epoxy-coated SiC/Si samples in aqueous solutions at various pHs at 60°C for selected times. Adhesion durability for the epoxy-coated SiC/Si systems was qualitatively evaluated by visual inspection to identify debonding and quantitatively evaluated with a probe test to determine the critical strain energy release rate, G _c . Durability via either test approach varied as a function of surface treatment in this manner: oxygen plasma treatment plus silane modification > silane treated > no treatment. X-ray photoelectron spectroscopic characterization of surfaces was carried out following the surface treatments and after complete adhesion failure in the durability tests. The XPS results suggested that improved performance was due to plasma cleaning and modification of the substrate surface, promotion of silane surface interaction, and the formation of a thicker oxide layer.