The Use of Peel Ply as a Method to Create Reproduceable But Contaminated Surfaces for Structural Adhesive Bonding of Carbon Fiber Reinforced Plastics

In the fabrication of fiber-reinforced plastics materials peel plies are commonly used as an additional layer on top of the laminates to sponge up the surplus resin and to create an activated surface for adhesive bonding or coating by peel ply removal. In theory, the peel ply removal results in a new and uncontaminated fracture surface that is activated by polymer chain scission. The peel ply method is often presented as being a good surface treatment for structural bonding.

In this study carbon fiber-reinforced plastics (Hexcel® 8552/ IM7) were produced by the use of five different peel plies and a release foil made of polytetrafluorethylene (PTFE). The peel plies themselves and the surfaces on the CFRP created by peeling were examined by scanning electron microscopy (SEM), x-ray photo electron spectroscopy (XPS), energy-dispersive x-ray spectroscopy (EDX), infrared (IR) spectroscopy, atomic force microscopy (AFM), and contact angle measurements to characterize the surfaces produced. Furthermore, the bond strength of lap shear and floating roller peel samples was determined with and without additional plasma treatment. For bonding, a room temperature-curing two-component-epoxy adhesive (Hysol® 9395) was used to prove the applicability of different peel plies for structural adhesive bonding under repair conditions.     

Protocols for the Measurement of Adhesive Fracture Toughness by Peel Tests

This article reports on the work of the European Structural Integrity Society Technical Committee 4 (ESIS TC4) and its activities in the development of test protocols for peel fracture. Thirteen laboratories have been working on peel test methods in ESIS TC4 since 1997 and their activities are ongoing.

The aim of the work is to develop robust and credible test methods for the determination of adhesive fracture toughness by peel tests. Several geometric configurations have been used, namely, multi-angle fixed arm peel, T-peel, and roller assisted peel in the form of a mandrel test.

The starting point of their work is an established analysis of a peel method that is often developed from a global energy approach. The adopted analysis is combined with an experimental approach in order to resolve ambiguities in the determination of adhesive fracture toughness (G _A ). The test methods involve the measurement of peel strength in order to calculate the total input energy for peel (G) and the calculation of the plastic bending energy (G _P ) during peel. The latter is often obtained from a measurement of the tensile behaviour of the peel arm. Adhesive fracture toughness is then G – G _P .

Four ESIS TC4 projects are described. The first relates to fixed arm peel whilst the second and third involve both fixed arm and T-peel. The fourth project combines mandrel peel and fixed arm peel. Each project uses different types of polymeric adhesives in the form of quite different laminate systems. The selection of the laminate system enables all characteristics of laminate property to be embraced, for example, thin and thick adhesive layers, polymeric, and metallic peel arms and a range of flexibility in the laminates.

The development of the enabling science required to establish the test protocols is described and software for conducting all calculations is referenced.     

Protocols for the Measurement of Adhesive Fracture Toughness by Peel Tests

This article reports on the work of the European Structural Integrity Society Technical Committee 4 (ESIS TC4) and its activities in the development of test protocols for peel fracture. Thirteen laboratories have been working on peel test methods in ESIS TC4 since 1997 and their activities are ongoing.

The aim of the work is to develop robust and credible test methods for the determination of adhesive fracture toughness by peel tests. Several geometric configurations have been used, namely, multi-angle fixed arm peel, T-peel, and roller assisted peel in the form of a mandrel test.

The starting point of their work is an established analysis of a peel method that is often developed from a global energy approach. The adopted analysis is combined with an experimental approach in order to resolve ambiguities in the determination of adhesive fracture toughness (G_A). The test methods involve the measurement of peel strength in order to calculate the total input energy for peel (G) and the calculation of the plastic bending energy (G_P) during peel. The latter is often obtained from a measurement of the tensile behaviour of the peel arm. Adhesive fracture toughness is then G - G_P.

Four ESIS TC4 projects are described. The first relates to fixed arm peel whilst the second and third involve both fixed arm and T-peel. The fourth project combines mandrel peel and fixed arm peel. Each project uses different types of polymeric adhesives in the form of quite different laminate systems. The selection of the laminate system enables all characteristics of laminate property to be embraced, for example, thin and thick adhesive layers, polymeric, and metallic peel arms and a range of flexibility in the laminates.

The development of the enabling science required to establish the test protocols is described and software for conducting all calculations is referenced.     

The Influence of Moisture Absorption-Drying of Composite Materials on the Bonding Performance of the Joints

Composite materials are susceptible to environmental threats correlated to moisture absorption, which affects  the bonding performance of the joints. Therefore, drying should be taken into account during actual manufacturing operations. In this work, the influence of moisture absorption-drying of composite materials on the bonding performance of the joints is investigated to provide a theoretical direction for the co-bonding process. Firstly, the surfaces of composite materials are treated with three methods: sanding, dry peel ply, and wet peel ply. Secondly, the composite materials are subjected to moisture absorption-drying treatment at 26 °C/65% relative humidity (RH) and 70 °C/85% RH. Finally, the above materials are bonded to evaluate the bonding performance. These results show that the bonding performance of the joints treated with two peel plies decreases significantly after moisture absorption. After moisture absorption-drying at 26 °C/65% RH, the bonding performance of the joints treated with dry peel ply cannot fully recover, while wet peel ply can be fully recoverable. However, the bonding performance of all joints cannot fully recover after absorbing moisture-drying at 70 °C/85% RH, whose recovery has relations with surface treatment.     

Comparison of Peel Tests for Metal-Polymer Laminates for Aerospace Applications

Standard peel tests for aerospace laminates based on metal-polymer systems, namely floating-roller and climbing-drum peel methods, have been accommodated in a unified theory of peeling. This theory also accommodates more basic peel tests such as T-peel and fixed-arm peel and also newer methods such as mandrel peel. These five methods have been applied to two aerospace laminate systems to critically examine their use in the determination of adhesive strength. The theory has been used to unify the outputs from the tests in terms of adhesive fracture toughness. In this way, the comparative merits of the methods can be commented on.

The validity of the standard methods has been put in doubt because of the absence of a correction for plastic bending energy and also because of the poor conformance of the peel arm to the roller system used in these methods. The unified theory and some measurements of peel-arm curvature help but not completely overcome some of these difficulties.

A further complication that arises in peel is a change in the plane of fracture. This reflects a transition from cohesive fracture in the adhesive to an adhesive fracture at the interfaces among adhesive, primer, and substrate. It is likely that such plane-of-fracture phenomena are intrinsic to evaluation of the laminate and that contemplation of cohesive fracture toughness for the adhesive cannot accommodate such events.     

Wettability and surface free energy of bovine serum albumin films

Measurements of the contact angle for water, glycerol, formamide, ethylene glycol, and diiodomethane on polymethyl methacrylate covered by adsorptive bovine serum albumin (BSA) films were made. Adsorption was performed from solutions in the concentration range 0–100 g/L. From the obtained contact angles the Lifshitz-van der Waals components and the values of the electron-acceptor and electrondonor parameters of the acid-based components of the films were calculated for six triplets of liquids. The biggest changes in the BSA film structure occurred under a monolayer coverage (i.e., at BSA concentrations of <2.5 g/L). On the basis of the contact angles of glycerol, ethylene glycol, and formamide it was concluded that the density of BSA polar groups was almost constant. The surface density of the hydrophobic part of the BSA film also seemed constant regardless of the concentration of the solution from which the BSA adsorptive film was created. This conclusion could be drawn from the almost constant contact angle of diiodomethane.     

竹材表面处理对胶合性能的影响

为提高竹材的胶合性能,用自制的偶联剂对竹材表面进行预处理,测试了处理前后表面接触角的变化,从而计算出竹篾外表面自由能及其分量的变化。将处理的竹篾压制成竹篾层积材,测试了竹篾层积材的物理及力学性能,并与未处理竹篾层积材进行了比较。研究结果表明,经偶联剂处理的竹篾表面自由能提高,压制的竹篾层积材的胶合强度也有明显的提高,还对偶联剂处理前后强度变化的原因进行了探讨。     

Experimental characterization of contact angle and surface energy on aramid fibers

In this paper, both contact angles and surface energy of aramid fibers are investigated using the liquid droplet method. First, the contact angles between matrix resin and aramid fibers are measured at different degrees of cure, which indicate that the contact angles increased initially and then decreased after the consolidation. Second, surface energy components of aramid fibers are determined from the contact angle using the geometric-mean equations. Finally, the influences of various surface treatments on the surface energy of aramid fibers are analyzed. These results play an important role for designing and evaluating the fiber/matrix interfacial strength of aramid fiber-reinforced composites.     

Wettability of Surface Oxyfluorinated Polypropylene Fibres and Its Effect on Interfacial Bonding with Cementitious Matrix

The surface of high molecular weight polypropylene monofilament fibre was modified using a oxyfluorination method. The oxyfluorination treatment level was varied and a hydrolysis post-treatment was also applied. Contact angles of oxyfluorinated, hydro-lyzed oxyfluorinated and unmodified polypropylene fibres were obtained by dynamic contact angle (DCA) measurement using three liquids of known dispersion, acid and base surface free energy components. The surface free energies were then calculated according to the acid-base theory developed by Good, van Oss and Chaudhury. Surface oxyfluorination largely increased the acid and base components of the fibres' surface free energy compared with unmodified polypropylene fibres. The oxyfluorinated and unmodified polypropylene fibre surfaces were observed by Scanning Electronic Microscopy and Photoacoustic Infrared Spectroscopy. It was found that the surface oxyfluorination largely increases the roughness of the polypropylene surfaces and the carbonyl group content increases as the treatment level increases. The interfacial shear bond strengths between the cementitious matrix and the polypropylene fibres treated under various conditions were determined by embedded fibre pull-out tests. Results showed that the fibre surface oxyfluorination treatments increase the interfacial bond strengths. The correlations between the shear bond strengths and surface free energy components were established. Results showed that fibre/concrete interfacial bonding was best correlated with the acid component of surface free energy of polypropylene fibres.     

Surface Characterization of Chlorinated Synthetic Vulcanized Styrene-Butadiene Rubber Using Contact Angle Measurements,Infra-Red Spectroscopy and XPS

The surface of a sulfur-vulcanized synthetic styrene-butadiene rubber (SBR) was treated with ethyl acetate solutions containing different amounts of trichloroisocyanuric acid (TCI). The chlorinated SBR surfaces were characterized using contact angle measurements (water, ethane diol, n-hexadecane), infra-red (IR) spectroscopy and XPS. Chlorination produced an increase of surface free energy which was mainly due to the enhancement of the acid-base component of the surface free energy, which remained almost unchanged when the amount of TCI was increased. Depending on the amount of chlorination agent, several chemical species were present on the SBR surface: i) For low amounts of TCI (up to 2 wt%), mainly chlorinated hydrocarbon and C – O species were present on the surface; ii) For medium amounts of TCI (between 2 and 5 wt%), an excess of unreacted TCI remained on the surface and a relatively small amount of isocyanuric acid was deposited; iii) For high amounts of TCI (larger than 5 wt%), a weak boundary layer (mainly composed of isocyanuric acid) was formed on the surface and thus the effects due to chlorination were decreased. There was good agreement between the experimental results obtained with contact angle measurements and XPS because both provided information on a surface region close to 100 Å, whereas IR spectroscopy results showed deeper penetration of the chlorinating agent into the SBR surface. The estimated thickness of the chlorinated layer was near 5000 Å as estimated from XPS measurements of SBR surfaces modified by argon ion bombardment.     

Plasma treatment effect on the surface energy of carbon and carbon fibers

The surface energy dispersive (γ^D_S) and polar (γ^P_S) components of carbon model surfaces (bal planes, prismatic surfaces, vitreous carbon) and of carbon fibers (high strength and high modulus, respectively) were determined systematically before and after plasma treatment. The method used is essentially based on the wetting contact angle measurements within two liquids. In all cases (γ^P_S) is markedly increased by the plasma treatment. For carbon fibers, with increasing plasma treatment duration (γ^P_S) is increasing toward a limiting value (-30 mJ/m²) while (γ^D_S) is depressed toward low values (-10 mJ/m²). The parallel evolution of surface topography is followed by SEM observations. The changes in surface energy of carbon model surfaces is also discussed.     

Time‐dependent changes of surface properties of polyether ether ketone caused by air plasma treatment

The effect of air plasma treatment on wetting and energy properties, surface composition and morphology of polyether ether ketone (PEEK) was investigated. The influence of the storage time on the surface properties of plasma‐treated polymer plate was also examined. The properties were determined by advancing and receding contact angle measurements, Fourier transform infrared spectroscopy supported by theoretical spectrum modelling, X‐ray photoelectron spectroscopy and optical profilometry. Three theoretical approaches were used in the determination of the apparent surface free energy of the untreated and plasma‐treated PEEK samples from the measured contact angles of probe liquids (water, formamide, diiodomethane): the contact angle hysteresis method, the Owens and Wendt approach and the Lifsthitz ? van der Waals acid–base approach. It was found that air plasma treatment of PEEK causes significant chemical and morphological changes of the polymer surface, which are reflected in the decrease of contact angles from 83.4° to 11.7° for water after 180 s plasma treatment. This is due to the formation of polar functional groups resulting in the increase of the surface hydrophilicity. After plasma treatment the apolar component of the surface free energy practically does not change, while the polar component increases significantly, especially for plates treated for 180 s, from 0 to 19.6 mJ m^?2. In addition, the modified PEEK surface is not stable during storage and it acquires more hydrophobic character. © 2016 Society of Chemical Industry     

激光和等离子处理对复合材料表面涂层附着力的影响研究

为了提高环氧涂料在纤维增强聚丙烯复合材料上的附着力,采用激光和等离子体表面前处理方法,应用超景深显微镜、粗糙度测定仪、接触角测试仪以及附着力测试仪,研究了激光和等离子体表面处理对纤维增强聚丙烯复合材料表面形貌、表面粗糙度和表面水接触角的影响,并且探究了这 2种表面处理方式对环氧涂层在复合材料上附着力的影响。结果表明： 2种处理方式均可明显提高环氧涂层在基材上的附着力,附着力均可由不到 1 MPa提高至 8 MPa以上。     

Acid/Base Components in the Molecular Theory of Adhesion

A method has been devised to determine the acid/base parameters of reference liquids as absolute numbers, and not as values relative to a conventional set of parameters for water. Contact angle measurements are employed, using three liquids on three solids. The theory calls for the solution of nine simultaneous, nonlinear equations in nine variables–and unreasonably formidable task.

A preliminary set of solutions has been computed, for one set of polar liquids on five solids. These results must be rejected on grounds of physical reasonableness. They also fail the test of predicting liquid-liquid interfacial tension, which for miscible liquids must be negative or zero.     

Acid/Base Components in the Molecular Theory of Adhesion

A method has been devised to determine the acid/base parameters of reference liquids as absolute numbers, and not as values relative to a conventional set of parameters for water. Contact angle measurements are employed, using three liquids on three solids. The theory calls for the solution of nine simultaneous, nonlinear equations in nine variables-and unreasonably formidable task.

A preliminary set of solutions has been computed, for one set of polar liquids on five solids. These results must be rejected on grounds of physical reasonableness. They also fail the test of predicting liquid-liquid interfacial tension, which for miscible liquids must be negative or zero.     

Adhesion phenomena in (co)extrusion coating of paper and paperboard

In extrusion coating, the inadequate adhesion between the polymer coating and the fiber-based paper substrate (paper and paperboard) is both a common and a constant problem. The lack of adhesion between the printing ink, or glue, and the polymer coating is another area where adhesion improvement is needed. The common means of improving adhesion are flame, corona, and ozone treatments. A modem extrusion coating line is equipped with both a pretreatment and a post-treatment unit. From the work presented here, the following observations were made. The higher the applied corona power and the thicker the coating, the higher the surface energy and polarity of the low density polyethylene (PE-LD) surface. When a high corona power was applied to the coating, only the polar component of the surface energy was increased. The surface energy decreased sharply as a function of aging, but remained more or less constant after about 2 weeks' storage time. The contact angles of water on paper correlated well with the oxygen contents (determined by ESCA) and with the applied corona power. The polarities of both paper and paperboard increased as a function of the applied corona power. Corona pretreatment of paper and paperboard improved their adhesion to PE-LD remarkably. The adhesion of the polypropylene (PP) homopolymer is based more on mechanical interlocking than on interfacial bonding. On the other hand, the oxidizing pretreatments of the paper substrates significantly promoted the adhesion of the PP copolymer.     

Evaluation of effects of non-thermal plasma treatment on surface properties of CAD/CAM materials

The purpose of this in vitro study was to evaluate the effect of the non-thermal plasma (NTP) treatment on the wettability and surface roughness of different types of CAD/CAM materials as well as the shear bond strength (SBS) of adhesive resin cement to the treated surfaces. Three different materials, namely; resin nano ceramic, feldspathic ceramic and poly(methyl methacrylate) (PMMA)-based samples were treated with NTP for different time points to evaluate the effect of NTP treatment on the surface properties of CAD/CAM materials. Moreover, surfaces of CAD/CAM materials were visualised with scanning electron microscopy (SEM). A 90-second NTP treatment time was determined as the optimum time for the highest measured wettability, and thus, the 90-second NTP treated samples were used for the SBS test and evaluation of the failure types. Our results revealed the NTP treatment lowered the contact angles and increased the roughness of all tested materials. Moreover, The NTP treatment significantly enhanced the SBS of resin nano ceramic and feldspathic ceramic-based materials. NTP could be considered as a novel pre-treatment method to improve surface properties and the bonding performance of ceramic-based CAD/CAM materials.     

Surface Analysis of Polymeric Joints

The stability of polymer-to-polymer joints was assessed using a thermodynamic method based on surface tension components, similar to that developed by Kinloch et al.,¹ showing that joint stability is improved in air by plasma treatments, while it is depressed in water. Shear strength tests showed qualitative agreements with these suggestions.

Surface analysis by contact angle measurements, SSIMS and XPS allowed the clarification of contributions which originated from phenomena unaccounted for by thermodynamic analysis. Plasma treatment was shown to form a weak boundary layer on polypropylene surfaces, possibly due to depolymerization. In the case of polycarbonate a water sensitive, possibly water soluble, layer is formed, therefore inducing a remarkable decrease in shear strength upon immersion in water.     

Atmospheric pressure plasma treatment of polyethylene via a pulse dielectric barrier discharge: Comparison using various gas compositions versus corona discharge in air

Modification of polyolefin surfaces is often necessary to achieve improved printability, lamination, etc. Although corona discharge and flame treatments can produce the higher surface energy needed for these applications, the properties of the resulting surfaces are not always optimal. Atmospheric pressure plasma is a surface modification technique that is similar to corona discharge treatment, but with more control, greater uniformity, and higher efficiency. Using an atmospheric pressure plasma unit with a dielectric barrier discharge generated using an asymmetric pulse voltage, the effects of different gases, powers, and linespeeds on polyethylene surface treatment were studied. Our results show that atmospheric pressure plasma can be used to achieve higher long‐term wettability, higher surface oxygen and nitrogen, and a greater range of surface chemistries with better robustness versus standard corona treatment. Atomic force microscopy results suggest significant differences in the mechanism of surface functionalization versus etching and ablation depending on the gases used. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 319–331, 1999