Adhesive joining of Aluminum A7075: effect of surface treatments

Di Bella G.1, Galtieri G. 2, Pollicino E.2, Borsellino C.3

CNR ITAE, Messina, guido.dibella@itae.cnr.it. University of Messina, Dep. of Industrial Chemistry and Engineering of Materials, Messina, epollicino@ingegneria.unime.it. 3 University of Messina, Dip. Ingegneria Civile, Messina, c.borsellino@ingegneria.unime.it.
2
1

Keywords: Adhesive bonding, Aluminum, Single Lap Joint

Extended Abstract
To optimise the adhesive joint performances it is necessary to pre-treat the metal surface, not only to remove contaminants, but also to provide the intimate contact needed for the adhesive to successfully bond with the adherent surface [1,2]. Pre-treatment is necessary to remove such contaminants, as lubricants and oils, and to provide the intimate contact needed for the adhesive to bond successfully with the adherent surface. The mere cleaning of aluminum surfaces is not suitable for their bonding due to the oxide layer that naturally occurs on exposure to air so we need to apply a more effective treatment (mechanical or chemical etching) to increase the adhesion capability of the substrates [3].
standard calomelan electrode A7075 sheet working electrode 30 mm 30 mm activated Ti counterelectrode

2 Stress [MPa]

Strain 0

a)

solution

b)

Fig. 1: a) Electrochemical etching; b) Typical Stress/Strain curve of the MS polymer based adhesive

In this work the effects of the substrate surface conditions on single lap aluminum joint properties were evaluated. Three different kinds of treatment were performed: - mechanical treatment [4] In order to remove either weak adhering or contaminated outer layers from the substrate surface, thereby, exposing the freshly oxidised bulk material directly to the adhesive, we performed a mechanical abrasion, enabling the formation of a suitable surface layer. This treatment is also useful in order to evaluate the effect of roughness on the joint resistance. Roughening using abrasive papers is common in many industries. The surface was prepared with three different grinding papers, identified by P80, P120 and P180. The 2.5% of the thickness was removed in order to obtain a regular surface. The residual particles remaining after mechanical abrasion were cleaned with pressurized air. - chemical etching [5] Two different chemical etching were realized on the aluminum sheets; an alkaline treatment and an acidic one, respectively with the following procedures: a. FPL etch pre-treatment: degreasing in acetone, hot water rinse, immersion in FPL etch solution (16.3 vol% H2SO4, 6 wt% Na2Cr2O7) for 20 min at 60C, 20 min rinse under tap water, drying with hot air stream; b. degreasing in acetone, then etching in 10 wt% NaOH solution for 50 s at 60C, rinsing under distilled water, and air drying. - electrochemical etching. Two different electrochemical attacks were realized on the aluminum sheets using the previous solutions. Fig. 1a reports the scheme of the electrochemical corrosion process. For the acidic solution a potential of 2 V (i.e. respect to the equilibrium potential) for 80 s was applied. For the alkaline one a potential of 1 V (i.e. respect to the equilibrium potential) for 50 s was applied. Both tests were carried out at room temperature. Aluminum A7075 sheets were used as a substrate. This very tough and durable alloy, made primarily from Zinc, Magnesium and Aluminum, is commonly used in aircraft and aerospace applications. The behaviour of this material was characterised by the experimental tests. Tab. 1 reports some properties. The sheet thickness was 4 mm. Two different adhesives were used: a MS polymer based adhesive (Fig. 1b shows the typical stress/strain curve) and an epoxy resin. Properties Value Yield stress [MPa] 470 Max stress [MPa] 530 Hardness [HV] 190 100-120 Grain diameter [m] Tab. 1: Properties of Aluminum A7075.

The single-lap joint tests, in according with standard ASTM D1002, were carried out to measure the resistance of the joints. Finally a data statistical analysis was performed to identify whether the surface treatment and the kind of adhesive are effective. The results show that the adhesive influence the behaviour of the joint. Whereas the influence of the treatment depends on the kind of adhesive that has been used.

References
[1] Wheeler M.J., Sheasby P.G., Kewley D., 1987. Aluminum structured vehicle technology - a comprehensive approach to vehicle design and manufacturing in aluminum, SAE Technical Paper 870146. [2] Bishopp J.A., 1988. The Adhesively Bonded Aluminium Joint: The Effect of Pretreatment on Durability, Journal of Adhesion 26(2-3), pp. 237-263. [3] Dinnie L., 1995. Sticking with it, Engineering (Vehicle Engineering and Design) 235(10), pp. 17-18. [4] Borsellino C., Di Bella G., Ruisi V.F., 2007. Effect of chemical etching on adhesively bonded Aluminum AA6082, Key Engineering Materials 344, pp. 669-676. [5] Borsellino C., Di Bella G., Ruisi V.F., 2009. Adhesive joining of aluminium AA6082: The effects of resin and surface treatment International Journal of Adhesion and Adhesives 29(1), pp. 36-44.

Adhesive joining of Aluminum A7075: effect of the surface treatments

Di Bella G.1, Galtieri G. 2, Pollicino E.2, Borsellino C.3
1

CNR ITAE, Messina, guido.dibella@itae.cnr.it. University of Messina, Dep. of Chimica Industriale e Ingegneria dei Materiali, Messina, epollicino@ingegneria.unime.it. 3 University of Messina, Dep. of Ingegneria Civile, Messina, c.borsellino@ingegneria.unime.it.

Abstract
In adhesive joining, pre-treatment of surfaces is necessary to remove a variety of contaminants, such as lubricants and oils providing an improved contact between the adhesive and adherents surface. Rather a specific surface treatment is required than a mere cleaning of aluminum surfaces for their bonding due to the oxide layer that naturally occurs on exposure to air. In this work the aluminum sheets were subject to several treatment of mechanical, chemical, and electrochemical nature. Specimen, like single lap joints were prepared applying two different adhesives: a MS polymer based and an epoxy resin. The impact on both substrates surface condition, produced by the treatments, and the kind of adhesive on single lap joint resistance were analysed. A design of experiments was defined in order to quantify the effect of the considered factors and their correlation. Keywords: Adhesive bonding, Aluminum, Single Lap Joint

1 INTRODUCTION
When an effective bonding technology with a relatively high strength/weight ratio and reduced cost is required the adhesive joining is being applied more and more, specially in aerospace and automotive industry. The choice of single lap joint with aluminium alloys and adhesive bonding connects light weight, simplicity and efficiency of realization. The adhesive bonding behaviour depends on many factors such as: physical and mechanical properties of both adherend and adhesive, geometrical parameters of the joints (like the overlap length, the overall length of sample, the thickness of the substrates and adhesive), the surface finish. The latter is one of the factors that influences the joint strength because the roughness leads to an increased contact area between the two substrates and increases the adhesion by mechanical interlocking [1]. Naturally we could expect that an increase in the surface roughness in the overlap area leads to an increase in the strength, regardless of the nature of the adhesive and of the adherends. However, research has confirmed that the relationship

between the joint strength and the substrate roughness is not only function of roughness but depends on other factors. For instance, to generate roughness some form of substrate pre-treatment induces physical-chemical changes affecting surface energy of adherends and then the wettability.[2-3]. The same surface treatments that improve adhesion have the effect of roughening the surface involved. Treatments, such as abrasion and etching, also remove weak boundary layers, increase the reactivity of the surface, and improve its wetting behaviour [4]. In this work the impact on both the substrate surface conditions and the type of adhesive on single lap aluminium joint properties was investigated. Three different kinds of treatments were performed: mechanical treatment, with three various grit blasting [5]; two different chemical etching, an alkaline treatment and an acid one [6]; electrochemical etching. The single-lap joint test was chosen to measure the joints resistance. A statistical data analysis was performed to determine whether the surface treatment is effective and if it depends on the adhesive choice.

2 EXPERIMENTAL SETUP
2.1 Materials Adherents Aluminum A7075 sheets were used as substrates. This very tough and durable alloy, made primarily from Zinc, Magnesium and Aluminum, is commonly used in aircraft and aerospace applications. The behaviour of this material was characterised by the experimental tests. Table 1 reports some properties. The sheet thickness was 4mm. Properties Yield stress [MPa] Max stress [MPa] Hardness [HV] Grain diameter [m] Value 470 530 190 100-120

Table 1. Properties of Aluminum A7075. Adhesives Two different adhesives were used: a) a MS (Modified Silane) polymer based adhesive, suited to bonding applications in the manufacture of boats, was used. To identify its characteristics, tensile experimental tests were carried out using an Universal Testing Machine model Lloyd, equipped with a 10 kN load cell. According to the ASTM 638M3 standard, three dog bone samples were tested applying a rate of 10 mm/min. Figure 1 shows the typical stress/strain curve. The trend is elastic-plastic. Table 2 reports the mean values of the mechanical properties.

b) an epoxy resin was mixed with slow hardener in 5:1 mix ratio by volume. Table 3 reports the main characteristics by producers datasheet.
2 Stress [MPa]

Strain 0 0 2 4

Figure 1: Typical Stress/Strain curve of the MS polymer based adhesive MS Adhesive Properties Stress [MPa] 1.56 0.1857 Strain 3.31 0.1478 E [MPa] 1.30 0.0612 Table 2. Mechanical properties of MS polymer based adhesive Epoxy Resin Properties Catalyst Catalyst quantity (%) Appearance Viscosity (25C 37 s-1) [P] Stability (darkness -20C) [month] Tensile Stress [MPa] Tensile Modulus [MPa] Elongation at break (%)

SD8822 31 Yellow 7.0 24 70 3000 3.8

Table 3. Epoxy resin properties 2.2 Surface Treatments Mechanical abrasion Mechanical abrasion was performed in order to remove either weak adhering or contaminated outer layers from the substrate surface. In such way the exposure of the freshly oxidised bulk material directly to the adhesive, was achieved, enabling the

formation of a suitable surface layer. Roughening using abrasive papers is common in many industries. The surface was prepared with three different grinding papers, identified by P80, P120 and P180. The 2.5% of the thickness was removed in order to obtain a regular surface. The residual particles remaining after mechanical abrasion were cleaned with pressurized air. Chemical etching Two different chemical etching were realized on the aluminum sheets; an acidic treatment (in the next A) and an alkaline one (in the next B), respectively with the following procedures: a) FPL etch pre-treatment: degreasing in acetone, hot water rinse, immersion in etch solution (16.3 vol% H2SO4, 6 wt% Na2Cr2O7) for 20 min at 60C, 20 min rinse under tap water, drying with hot air stream; b) degreasing in acetone, then etching in 10 wt% NaOH solution for 50 s at 60C, rinsing under distilled water, and air drying. Electrochemical etching Two different electrochemical attacks were realized on the aluminum sheets using the previous solutions A and B. Figure 2 reports the scheme of the electrochemical corrosion process. For the acidic solution a potential of 2 V (i.e. respect to the equilibrium potential) for 80 s was applied. For the alkaline one a potential of 1 V (i.e. respect to the equilibrium potential) for 50 s was applied. Both tests were carried out at room temperature. In the next the samples electrochemically treated will be named EA and EB, respectively.
standard calomelan electrode A7075 sheet working electrode 30 mm 30 mm activated Ti counterelectrode

solution

Figure 2: Electrochemical etching

2.3 Roughness Measurements A surface profiler, a RTH Form Talysurf, was used to determine the roughness parameters, both before and after the surface treatment. The profiler moves along a single direction with a scanning length of 2.5 mm. Measurements were performed in different areas of the same surface, along two different directions (i.e. parallel and orthogonal to the sheet axis), in order to verify the treatment uniformity; the average roughness values Ra were calculated. The experimental results showed small spreads, i.e. the variability in the measured Ra values was always lower than 10%. 2.4 Single Lap Joint Tests A wide variety of joint configurations are possible when bonding structures. The single-lap and double-lap configurations are the most commonly found in practice and are applicable for joining relatively thin adherents (i.e. 4 mm); on the other hand, the more advanced stepped lap and scarf configurations are used to transfer high loads in joint with thicker adherents. For these last the manufacturing is more complicated, requiring low machining tolerances. Since the single-lap joint is generally the simplest and cheapest of all joints to manufacture due to its simple design and easy assembly, it was chosen for the test according to the standard ASTM D1002 for the determination of joint shear strength. The mean shear stress is evaluated by the formula:

P A

(1)

where P is the tensile load and A is the joint overlap area. Figure 3 reports the joint configuration. The sheets sizes were: length of 100 mm and width of 25 mm. The area of overlap zone was 25x25 mm2. The adhesive thickness was 0.1 mm.
Constrained from all displacements

Overlap zone

Figure 3: Joint configuration The procedure for the samples preparation was the following: firstly, a thin layer of adhesive was applied on the surface of the adherents using a brush, then the substrates were aligned and a pressure was applied with clips, to squeeze out the extra adhesive, until the standardised thickness was obtained. The thickness was measured with a 1/100mm precision calliper. Moreover, the samples were realised under extractor fan, at constant and controlled temperature, and then tested when curing time of both adhesives was fully completed. Universal Testing Machine model Lloyd, equipped with a 10 kN load cell and with tensile clamps, was used.

2.5 Statistical Analysis To verify if the surface treatment is a significant factor that influence the mechanical properties of the joint, a statistical analysis (ANOVA) was performed using Minitab software.

3 RESULTS AND DISCUSSION

3.1 Roughness Measurements The measured roughness values are reported in Table 4. Obviously the mechanical treatments induce the higher roughness, but also chemical etching is no less. The different values, observed between parallel and orthogonal, are due to the manufacturing process of aluminum sheet (i.e. rolling). Treatment No treatment Mechanical P180 Mechanical P120 Mechanical P80 Acidic Alkaline Electro-acidic Electro-alkaline Ra [m] parallel orthogonal 0.095 0.178 0.68 0.83 1.07 1.11 2.06 3.73 1.21 1.29 1.21 2.35 0.25 0.41 0.173 0.26

Table 4. Ra mean values 3.2 SINGLE LAP JOINT TESTS A typical stress/displacement curve for a bonded sample mechanically treated with the grinding paper shows, after an initial settlement, a normal elastic-linear trend. When the stress continues to increase, the trend is not linear because the adhesive starts to plastically deform. After the reaching of the maximum value, the opening of the joint occurs. Figure 4 e Figure 5 resumes the results obtained for all the tested joints with both adhesives. The electrochemical etching does not affect strongly the mechanical properties of joints, it is comparable to no treatment.

Stress [MPa]

4 3 2 1 0

mechanical

chemical

electro

NT

P180 P120 P80

EA

EB

Figure 4: Max Stress of adhesively MS polymer bonded joints

14 12 10 8 6 4 2 0 NT P180 P120 P80 A B EA EB

Stress [MPa]

mechanical

chemical

electro

Figure 5: Max Stress values of epoxy bonded joints In the set of bonded samples with the MS polymer based adhesive, the mechanical treatments induce an improvement of the mechanical properties higher than both chemical and electrochemical etching. The values of max stress for all surface treatments are within same range between 2 3 MPa. It shows that the joint strength is influenced by the elastic-plastic behavior of the type of adhesive and it increases with the mechanical treatment. The group of adhesively epoxy resin bonded joints shows stress higher than previous set, 4 10 MPa. Also here the mechanical surface roughness enhances the adhesion. It is possible to observe that the in alkaline solution etched samples present the

highest stress value. This treatment dissolves the natural alumina layer, activates the aluminum surface and helps in generation of a new porous alumina layer that will well adhere [7]. In the latter oxide film the presence of MgO, thermodynamically passive in alkaline environment, interacting with the resin/alkaline hardener system, produces better adhesive properties than mechanical treated joints. Figure 6 shows some typical failure of the tested samples. Figure 6a e Figure 6c show the debonding surfaces observed for the mechanically treated samples. The failure does not occur within the adhesive, but interests also the interface adherent/adhesive. The better properties are due to the higher roughness of the adherents. In fact for the presence of the peaks, induced on the surface by the grinding papers, the thickness is locally reduced. This reduction influences the joint resistance that increases [9]. This behaviour has been observed also in previous works studying a commercial aluminum, mechanically treated [8]. Figure 6b e Figure 6d show the failure that characterises the chemically treated samples. In Figure 6b the failure is fully cohesive and for this fact the properties are higher than the not treated specimens. The presence of an oxide layer, porous and well adhered, on the aluminium alloy is necessary to enhance the adhesive strength. In Figure 6d the failure occurs mainly at the interface in adhesive way, but not cohesive due to the brittleness of epoxy resin. In the mechanical treatment the surface roughness strengthens the joint, but in the alkaline process the change of oxide layer improves the adhesion although the roughness is low.

a)

c)

b)

d)

Figure 6: Failure modes obtained with MS polymer (left) and epoxy resin (right) adhesives: a)/c) mechanical; b)/d)chemical.

3.2 STATISTICAL ANALYSIS Table 5 reports the results of the variance analysis that allows to verify the significance of the parameters (i.e. treatment and adhesive). It is possible to observe that both the parameters are significant factors (P<0.05). Source DF SS MS F Treatment 7 144,263 20,609 40,14 Adesive 1 370,316 370,316 721,34 Treatment*Adhesive 7 116,720 16,674 32,48 Error 64 32.856 0,513 0.513 Total 79 664.155 S = 0.716502 R-Sq = 95.05 % R-Sq(adj) = 93.89% Table 5. ANOVA.
11 10 9 8 Mean 7 6 5 4 3 2 1 Adhesive 2
Treatment 1 2 3 4 5 6 7 8

P 0.000 0.000 0.000

1 2 3 4 5 6 7 8

NT P180 P120 P80 A B EA EB

Figure 7: Interaction plot for Stress [Mpa], for 1=MS Polymer adhesive, 2=Epoxy resin. In effect, analysing the data, it is possible to observe (see Figure 7) that for the joints with MS polymer the treatment is not a significant parameter, then the interaction between adhesive and treatment is to be intended that, only employing the epoxy resin for bonding, the treatment can improve the joint resistance. Moreover it is evident also that the stress values, with varying the adhesive, belong to two different populations. Finally, the interaction is significant as observed by the analysis of the failure modes.

5 CONCLUSIONS
The experimental results, analysed statistically, show that the treatment is a significant parameter, that influences the resistance of a single lap joint, as a function of the used adhesive. In particular it is possible to draw out that: - Aluminum AA7075 joints bonded with MS polymer are characterised by: low mechanical resistance, cohesive fracture and their resistance is not influenced by the surface treatments; - on the converse when the joints are bonded with epoxy resin they are characterised by: high mechanical resistance with different failure modes as a function of the treatment. In particular mechanical treatment and alkaline etching induce the better properties.

REFERENCES
[1] Petrie, E.M., 2000. Handbook of adhesives and sealants, New York: McGrawHill, New York. [2] Reina, J.M.A., Prieto, J.J.N., Garca, C.A., 2009. Influence of the surface finish on the shear strength of structural adhesive joints and application criteria in manufacturing processes, Journal of Adhesion, 85, pp. 324-340. [3] Da Silva, L.F.M., Ferreira, N.M.A.J., Richter-Trummer, V., Marques, E.A.S., 2010. Effect of grooves on the strength of adhesively bonded joints, International Journal of Adhesion & Adhesives, 30, pp.735-743. [4] Packham, D.E., 2003. Surface energy,surface topography and adhesion, International Journal of Adhesion & Adhesives, 23, pp.437-448. [5] Borsellino, C., Di Bella, G., Ruisi, V.F., 2007. Effect of chemical etching on adhesively bonded Aluminum AA6082, Key Engineering Materials, 344, pp. 669-676. [6] Borsellino, C., Di Bella, G., Ruisi, V.F., 2009. Adhesive joining of Aluminum AA6082: The effect of resin and surface treatment, International Journal of Adhesion and Adhesives, 29, pp. 36-44. [7] Prolongo, S.G., Urena, A., 2009. Effect of surface pre-treatment on the adhesive strength of epoxy-aluminium joints, International Journal of Adhesion and Adhesives, 29, pp. 23-31. [8] Da Silva, L.F.M., Carbas, R.J.C., Critchlow, G.W., Figueiredo, M.A.V., Brown K., 2009. Effect of material, geometry, surface treatment and environment on the shear strength of single lap joint, International Journal of Adhesion and Adhesives, 29, pp. 621-632. [9] Di Bella, G., 2009. Experimental and numerical study of bonded joints with polyurethane and MS polymer based adhesives subjected to in-plane and outof-plane loads, Proceedings IX AITEM, Torino.