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ADHESION OF SILICONE COATINGS TO POLYPROPYLENE FILMS

Lesley-Ann OHare, Stuart R. Leadley, Bhukan Parbhoo, John G. Francis

50

40

Surface Energy (mJm-2)

Dow Corning Ltd., Cardiff Road, Barry, Vale of Glamorgan, CF63 2YL, UK The aim of this work was to elucidate the mechanisms of adhesion of a silicone coating to a corona discharge treated polypropylene (PP) film. A physico-chemical study of the PP surface utilising contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM) was carried out. These techniques were used to probe changes in the surface energy, surface chemistry and surface morphology, and the results were related to practical adhesion data. Surface energies investigated the role of physisorption, whilst chemisorption was examined by the surface chemistry changes. The presence of mechanical interlocking was studied by changes in the morphology, and a combination of these techniques on washed samples scrutinised the presence of a weak boundary layer.

Introduction.

30 -2 Polar Contribution (mJm ) 20 -2 Dispersive Contribution (mJm ) -2 Total Surface Energy (mJm )

10

0 0 2 4 6 8 10 12 14

Corona Energy (kJm-2)

Experimental
Materials. The film used in this study was 30 m thick, biaxially oriented polypropylene (BOPP). The film was previously untreated, with no surface contamination observed by X-Ray Photoelectron Spectroscopy. The contact liquids used were water (HPLC Grade Fisher); formamide (99.5+% - Acros); diiodomethane (>98% - Fluka); ethane-1,2-diol (>99.9% Acros). The silicone coating system used reacted via addition cure chemistry, comprising a vinyl- and a hydride-functional silicone polymer. Equipment. Corona discharge treatment (CDT) was carried out on a GX10 corona treater, manufactured by Sherman Treaters, Thame, Oxon. The films were exposed to one pass under an electrode of width 0.4m, in ambient air at a speed of 10 mmin-1. The various power settings used were converted to energy values. Contact angles of sessile drops were measured using an Advanced Surface Technology video contact angle VCA2500 system. Contact angles were measured on the modified side of the PP films within twenty minutes of treatment. The surface energy results presented are the average of three experiments carried out on consecutive days. The method of calculation used in this study was the geometric mean approach of Owens-Wendt1 and Kaeble2. X-ray Photoelectron Spectroscopy was performed using a Kratos Analytical Axis Ultra instrument. A monochromated Al Ka X-ray source was used at a nominal power of 300 W to record spectra at normal emission. All of the samples under consideration required charge compensation. Atomic Force Microscopy was carried out on a Digital Instruments Dimension 3100, in the TappingMode using a silicon tip. Both height and phase images of scanned area 1 m2, 25m2 and 400m2 were captured.

Figure 1. Surface Energy ( ) and its polar ( p) and dispersive ( d) components of corona discharge treated polypropylene film as a function of corona energy As would be expected for a polypropylene film, the survey spectrum showed carbon to be the main element present at the surface of the untreated film. Survey spectra acquired from the corona treated films showed carbon and oxygen to be the only elements present at the surface. This indicates that the polar groups introduced by CDT contain oxygen. The amount of oxygen incorporated typically increased with increasing corona energy. Between 5 and 11% atomic oxygen is introduced to the surface over the energy range studied. By fitting peaks to the high-resolution C 1s spectra, it was also possible to identify the specific type of functional groups introduced at the surface by CDT. Corona treatment introduces a shoulder on the high binding energy of the C 1s spectrum, Figure 2.

Results and Discussion


Physical Adsorption Theory. Surface energy () measurements interrogate the polar (p) and dispersive (d) components of a substrate. The role of the physical adsorption theory in adhesion of silicone to BOPP film can thus be investigated. Figure 1 shows the values obtained for , p and d plotted as a function of the energy delivered to the surface of the polypropylene film by corona discharge. Before CDT, the surface energy of the polypropylene film is composed solely of a dispersion component. As expected, and p increase with increasing energy of CDT. However, the shape of the curve for p is not the same as that of . This indicates that at certain CDT energy levels (2.25 to 4.05 kJm-2), the surface energy does not correlate with the increase in polarity alone. Since the dispersive component remains relatively constant across the energy range studied, including the untreated film, enhanced adhesion after CDT is not caused by the physisorption mechanism. Chemical Adsorption Theory. The chemisorption theory was probed by monitoring the changes in the surface chemistry of the BOPP due to CDT. The introduction of any functional groups to the surface of the BOPP that could interact with the silicone coating would imply that chemical adsorption was an important mechanism of adhesion. b

Figure 2. High resolution spectra of polypropylene film a) untreated film, b) treated film, corona energy = 15 kJm-2 In agreement with studies published elsewhere3,4,5, this work has assigned the functional groups introduced by CDT of BOPP as hydroxyl, carbonyl, peroxy, ester, carboxylic acid and anhydride groups. It was observed that the number of peaks that could be fitted, and their relative areas, varied depending on the energy of corona discharge. At lower energy levels it was not possible to fit all six additional peaks. It is proposed, therefore, that the type of functional groups introduced to the surface of polypropylene films, and their relative concentrations, are dependant on the energy delivered to the surface by CDT. The changes in the relative concentrations of the species introduced are presented as a function of the energy of corona in Figure 3.

Polymer Preprints 2001, 42(1), xxxx

Table 1. Roughness values for a series of corona treated polypropylene films.


3.5

Relative Concentration (%)

3
C-OH

Corona Energy (kJm-2) RRMS (nm)

0 2.4

3.15 2.2

5.70 2.6

15.0 4.2

2.5 2 1.5 1 0.5 0 0 5 10 15

C-O-O C=O C-O-C*=O HOC=O C(O)OC(O)

To try to avoid ambiguities regarding the fractal nature of the surface, and any changes in roughness that may incur, all roughness values were calculated on a 1 m2 area. It is clear that under these conditions no significant increase in roughness occurs. Previous studies that reported an increase in roughness by CDT utilised longer treatment times and higher powers. This suggests that in the case of silicone adhering to polypropylene film, mechanical interlocking is not a dominant mechanism of adhesion. Weak Boundary Layer. The formation of a layer of low molecular weight oxidised material (LMWOM) on the surface of PP film after CDT is widely accepted7. It is the effect of the material on adhesion that is debated. The formation of a weak boundary layer may be beneficial or detrimental to adhesion, dependant on its solubility in the adhesive matrix. If the layer is soluble in the matrix, no decrease in adhesion may be observed. If, however, the layer is not soluble, this may reduce adhesion due to the presence of this cohesively weak layer at the interface. Water washing experiments were carried out to evaluate the effect of LMWOM on the surface chemistry and morphology. XPS and AFM analyses were carried out under the same conditions as used for the unwashed samples. XPS identified that around 50% of the oxidised material on the surface is in the form of water-soluble LWMOM. Since after washing the atomic oxygen content does not decrease to that of the untreated film, this indicates that some of the oxygen incorporated is firmly bound to the polymer backbone. AFM also reinforces the theory that not all the material is removed by washing, since although the globular morphology observed in Figure 4b is removed, the structure does not return to that of the untreated film, Figure 4a. The amount of LMWOM removed by water washing varies with the energy imparted to the surface of the film. The greatest change is observed on the film treated at the highest corona energy. It is possible that the presence of this material may form cohesively weak layer at the interface that is insoluble in the silicone adhesive matrix. Thus weak boundary layer is an important mechanism in the adhesion of silicone to CDT polypropylene. Practical Adhesion Measurements. The anchorage of the silicone coating to the film has been evaluated using the anchorage index test. The test was carried out on films treated at all CDT energy levels, with siliconising being carried out of films both with and without water washing. The results clearly showed that removal of LMWOM by water washing prior to siliconising is beneficial to adhesion over a 1 month time period, particularly at the highest treatment energy. The effect of corona discharge treatment on the surface physicochemistry of biaxially oriented polypropylene has been investigated using surface energy measurements from contact angles, X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. The information gathered from these techniques, in addition to practical adhesion measurements, has enabled identification of the dominant mechanisms of adhesion of silicones to PP films. The physisorption mechanism and the mechanism of mechanical interlocking are not the cause of enhanced adhesion after corona discharge treatment in this system. It is believed that the dominant mechanisms of adhesion of silicone to corona treated polypropylene are chemisorption and weak boundary layer.

Corona Energy (kJ/m2)

Figure 3. The functionalities introduced by Corona Discharge Treatment as a function of corona energy Hydroxyl, peroxy and carbonyl functional groups are introduced at all levels of CDT. The more highly oxidised species, however, are not introduced until more aggressive energy levels have been employed. More surprisingly, these carboxylic acid, ester and anhydride groups increase in concentration at energy levels where the atomic concentration of oxygen is actually decreasing slightly. This suggests that until the energy level of ~ 4 kJm-2 is crossed, the main mechanism of CDT is oxidation and crosslinking; above this energy level, a chain scission mechanism is also occurring. The chemisorption mechanism of enhanced adhesion must be of importance; the nature of such functional groups as discussed previously may affect the performance of any particular adhesive system. This is likely to be true for this type of reaction; the highly reactive Si-H species in the adhesive may react with functional groups on the surface. This supposition has yet to be confirmed, and further work will be necessary to determine any rates of reaction that may occur. These results must also be compared in turn with the rate of hydrosilylation of the vinyl functional groups in the bulk silicone Mechanical Interlocking. Increased practical adhesion after CDT has often been attributed to mechanical interlocking due to increased roughness. AFM was used to monitor any morphological changes induced by CDT, and then to relate these to any variation in the adhesive properties of polypropylene film. The biaxial orientation of the untreated film, as observed by Boyd et al6 was apparent in the 1 m2 image. The defined fibrillar structure often commented on for untreated PP was observed, Figure 4a. After CDT, however, a different morphology emerges; globular features of 50 100 nm diameter are observed, Figure 4b. At energy levels between 0 and 5.7 kJm-2, both the fibrillar and globular morphologies can be observed, due to the heterogeneity of the treatment at low energy levels. Figure 4c shows again a different morphology. In this image, a branchlike structure is observed. It may be surmised that at this high energy level the treatment is exposing the underlying polymer structure. The low molecular weight boundary layer common to polyolefins, and perhaps parts of the amorphous regions, has been ablated under these conditions.

Conclusions

References
1

Figure 4: AFM images of polypropylene film a) 1 x 1 m untreated, b) 1 x 1 m treated film, corona energy = 5.70 kJm-2, c) 5 x 5 m treated film, corona energy =15.0 kJm-2 In addition to observing the changes in morphology, the root mean square roughness (RRMS) was also calculated, Table 1.

Owens, D.K.; Wendt, R.C. J. Appl. Polym. Sci. 1969 , 13, 1741 Kaeble, D.H. J.Adhesion 1970 , 2, 66 3 Foersch, R.; McIntyre, N.S., J. Polym. Sci.: Part A: Polym. Chem. 1990 , 28, 193 4 Comyn, J., Adhesion Science , Ch.1, RSC Paperbacks 5 Mayoux, C.; Garcia, G.; Sarlaboux, J., IEEE Trans, Elec. Insulation 1982 , 17(2), 156 6 Boyd, R.D.; Kenright, A.M.; Badyal, J.P.S., Macromolecules 1997, 30, 5429 7 Strobel, M.; Dunatov, C.; Strobel, J.M.; Lyons, C.S.; Perron, S.J.; Morgen, M.C., J. Adhesion Sci. Technol, 1989, 3(5), 321-335,
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Polymer Preprints 2001, 42(1), xxxx

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