DURABILITY STUDY ON FRP LAMINATES

Sookay, N.K.*, von Klemperer, C.J. and Verijenko, V.E.

School of Mechanical Engineering, University of KwaZulu-Natal, Durban, 4041. *Corresponding author: Tel: +27 31 260 3207. E-mail: sookayn@ukzn.ac.za

ABSTRACT
There is at present a lack of reported data characterising the response of long term exposure of FRP composites to the natural environment in Southern Africa. Outdoor exposure tests are required to determine the mode and speed of degradation of these materials exposed in the local environment. Performance in new service environments are required to optimise the design and maintenance schedules of FRP structures. The most reliable method of determining the behaviour of materials in the service environment at present is to expose the material to the environment and remove specimens periodically for sampling and testing. Six test sites, at which FRP laminates have been exposed, have been identified to represent the range of environments experienced in Southern Africa. Laminates are removed bi-annually for inspection and testing. Laminates exposed after 67 weeks of exposure experienced a loss of material from the surface exposing the fibres below. Mechanical tests have been performed to quantify the change in mechanical properties.

INTRODUCTION
Outdoor exposure tests are required to determine the long term performance of the FRP composites in the natural environment. The expected performance of the material is required at both the design stage and during service. Exposure tests have been performed in foreign climates but there has been no reported data from exposure tests conducted in Southern Africa. There is therefore a lack of data describing the performance of FRP composites locally. At the design stage the decrease in strength due to exposure needs to be known in order to ensure that the structural integrity of the structure is not compromised during the life of the component. Accurate data is required to prevent over-design of the structure thereby maximising the strength to weight ratio advantage of FRP composites over traditional materials. Failure to consider the reduction in strength due to degradation may result in premature or even catastrophic failure. Failure with the included down time proves costly and reduces the return on investment. During the service life of the structure, degradation factors need to be understood in order to optimise maintenance schedules. Unnecessary maintenance proves costly while lack of maintenance may result in potential failures not being repaired in time. To determine the long term performance of material in the end use environments, exposure tests have been undertaken in Europe and North America (1). The tests were performed over a period of ten years and provide a trend of the change in mechanical properties with time. Similar tests were reported by Chester and Baker (2) on epoxy composites exposed in the tropical environments of Australia and Malaysia. Unprotected laminates were found to rapidly degrade on exposure to UV radiation therefore shading of equipment in which the composites would be used was recommended. Fukuda (3) has reported on outdoor exposure tests performed in Japan. Exposure tests in the warm humid conditions at the Black Sea have been reported by Startsev and Krotov (4) in which the efficiency of a diffusion model was demonstrated. Exposure tests have therefore been reported on multiple exposure sites across the world with the aim of determining the long term performance of polymeric composites at specific locations. The various climates experienced in South Africa has been studied and exposure test sites identified in differing climates. GFRP laminates have been manufactured and placed at the
Proceedings of the 2nd Biennial International Composites Africa ISBN Number: 1-920-01720-8 Proceedings produced by: Document Transformation Technologies cc 24 25 August 2004 Johannesburg, South Africa 420

exposure test sites. Laminates are removed bi-annually for inspection and testing with the aim of identifying predominant degradation mechanisms and quantifying the rate of degradation. The data from these tests will be used as an input into a mathematical model to predict the long term performance of the material. A model is being developed for this purpose by considering the progression of damage from the surface of the laminate to the interior.

METHOD
Two different aerospace grade epoxy systems were used to manufacture the epoxy laminates. Epoxy 1 is a prepreg with the reinforcement being 8-harness stain weave glass fibre. These laminates were manufactured with nine layers of material and cured in an autoclave. Epoxy 2 was a wet lay-up system that was reinforced with 22 twill weave glass fibre of arial weight 290g/m2. Laminates were manufactured by hand lay-up using ten layers of reinforcement. Upon curing, the laminates manufactured by wet lay-up were post cured as per manufacturers instructions. Isopthalic polyester laminates were also manufactured using a similar hand lay-up technique. Vinylester and orthophthalic polyester laminates were hand laid and then placed under compression to improve compaction. The edges of the laminate were free allowing excess resin at the centre to flow towards the edges. The vinylester and both polyesters were post cured in a thermofan oven according to manufacturers instructions. Laminates were cut from the prepared sheets to specimen sizes of 15050mm for mounting onto the outdoor exposure panels. The climate in South Africa was examined to identify climatically differing regions that would affect degradation of the laminates. Nine possible regions had been identified and this has since been reduced to six exposure locations. The exposure locations represent the range of climates ranging from hot, wet to cold and dry conditions. The positions of the test locations are illustrated in Figure 1. The exposure panels were designed and manufactured from a steel frame and stainless steel backing. The covering panel on the frame has cut-outs of dimensions 13040mm through which the laminates receive their exposure. The framed exposure was decided upon as it does not require the edges of the laminate to be separately sealed. Edge effects of the exposure are therefore minimised.

Figure 1. Exposure locations in Southern Africa.

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Laminates are mounted with the mould surface of the laminate at an angle of 30 to the horizontal. This angle was used as it represents the average latitude angle of South Africa, therefore exposure at this latitude angle maximises the solar irradiance to which specimens are exposed. Exposure panel mounting fixtures were required to secure the exposure panels at 30 to the horizontal as shown in Figure 2.

Figure 2. Exposure panels mounted at a test location. Specimens were removed for examination and testing after 10 and 20 weeks of exposure to determine the transient changes that occur during initial stages of exposure. Thereafter laminates were removed bi-annually for examination and testing. The bi-annual sampling is done during the summer and winter months and thus represent the range of climatic conditions to which the laminates are exposed at a particular location.

SCANNING ELECTRON MICROSCOPY EXAMINATION

Images were captured during Scanning Electron Microscopy (SEM) examination of epoxy laminates. Figure 3 and 4 are images of epoxy 1 laminate. Figure 3 represents a typical crosssection of unexposed specimens. No irregularities have been observed. The resin layer above the fibres is approximately 15m thick at the thinnest section. The thinnest section of resin at the laminate surface was found to occur at regions above the longitudinal weave.

Figure 3. Cross-section of unexposed laminates. After 67 weeks of exposure, resin at the surface of the epoxy appears to have been eroded, leaving underlying fibre exposed as evident in figure 4. The resin appears to have been eroded to the depth of half the longitudinal weave, approximately 0.1mm thick. There appears to be no damage on the fibres or residue of resin on the fibres. No significant cracking has been observed on the matrix.
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Figure 4. Cross-section of epoxy 1 laminate after 67 weeks of exposure. Cracks have been noticed on the surface of epoxy 2 as evident in figure 5. From examination of the image of the cross-section of the laminate, most surface cracks appear to occur in a thin layer at the surface of approximately 15m in depth. In addition to these cracks, a few larger cracks, approximately 40m in length, have been observed propagating from the surface towards the centre of the laminate. At this stage of exposure, cracks originating at the surface do not appear to have reached the layer of fibres closest to the surface. No loose fibres on the transverse weave have been exposed to the environment due to loss of the surface layer of resin at this stage of exposure.

Figure 5. Damage on the surface of epoxy 2.

Figure 6. Fracture of resin at the surface of a laminate.

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The fracturing of a weathered layer of surface resin is evident from Figure 6. The surface layer has been worn to a thickness of approximately 20m from an initial thickness of 100m. Cylindrical cavities are visible on the fibre side of the damaged surface layer of resin. Multiple cracks on the eroded surface layer and between the fibres in the weave are also visible. Loose fibres are visible below the damaged surface layer of resin.

COMPRESSIVE STRENGTH RESULTS

The results of compression tests were analysed and are presented as a fraction of the strength of unexposed laminates by the ratio /0, where is the strength of the laminate measured after twenty weeks of exposure and 0 is the strength of the unexposed laminate. This facilitates comparison of the change in strength as the value of approximately one indicates no change in strength, values greater than one indicate an increase in strength and values less than one indicate a decrease in strength. The scatter of values of unexposed laminates are located in a region of 5.3% from the average. After twenty weeks of exposure, laminates at Alkantpan and Durban appear to be most affected by exposure as illustrated in Figure 7. Laminates exposed at Alkantpan have been most affected by exposure as these laminates have experienced an average loss of approximately 10% of the original compressive strength. The data does however contain a large scatter indicating that not all test specimens were equally affected. Specimens exposed at Durban have lost approximately 7% of their original strength. Laminates exposed at Irene appear to be least affected by twenty weeks of exposure with only a 2% decrease in strength.
Relative compressive strength of epoxy 1 specimens after 20 weeks of natural exposure
1.2 1 0.8

/0

0.6 0.4 0.2 0

Irene

Alkantpan

Durban

Figure 7. Compressive strength of epoxy 1. The scatter of values of unexposed epoxy 2 laminates are within a region of 5.7% of the average. Laminates exposed at Irene and Durban appear to be equally affected by exposure to the environment, Figure 8, with a strength loss of 6% being measured. Laminates exposed at Alkantpan appear to not have been affected by exposure, as the average compressive strength has not measurably changed.

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Figure 8. Compressive strength of epoxy 2.

DISCUSSION
Results have been presented for epoxy specimens only as vinylester and polyester laminates are currently being examined and tested. When unexposed laminates were examined, they revealed a thin layer of resin present at the mould surface. The thickness of the surface resin was taken as the minimum distance from the surface of the laminate to the fibres closest to the surface. This surface layer of the resin is dependent on the manufacturing technique. The largest layer of surface resin, of approximately 100m, was found on laminates manufactured by hand lay-up. The thinnest layers, of approximately 15m, of surface resin was found on laminates cured and compacted in an autoclave. The pressure applied to the laminate in an autoclave would ensure effective compaction and thus minimise the layer of resin at the surface and within the laminate. Autoclave cured laminates therefore have a higher fibre-volume ratio than laminates manufactured by hand lay-up. The presence of the layer of resin at the surface, as a consequence, protects the fibres below. A thick surface layer of resin may not imply that the fibres below will be protected for longer duration as erosion of the surface layers progresses. The erosion rate of the surface needs to be established before any prediction can be made us to when the fibres closest to the surface become exposed. Resins with a higher resistance to weathering may offer fibre protection for a longer duration. As the duration of exposure progressed, the surface layer of the laminates were eroded to an extent that the fibres below had become exposed, Figure 4. Examination of the cross-section of epoxy 1 laminates after 67 weeks of exposure reveals fibres that do not appear to have any remaining residue of matrix attached. This may be due the abrasion caused by the relative movement of fibres against each other once the fibres had become completely exposed and loose. Lack of residue on the fibres could also be due to the fibre-resin interface having been disrupted. Hammami and Al-Ghuilani (5) have observed spots of resin on degraded laminates subjected to durability testing. The rate of erosion of the resin from the surface of the laminate may decrease when compared to the initial rate of erosion as exposed fibres may protect the resin from the environment. Fibre exposure has been noticed by Dubois et al (6). Cracking of the laminate surface has been observed on epoxy 2 in contrast to epoxy 1 where no significant surface cracks were observed. The average depth of surface appears limited to the surface with the average crack depth being 15m. These surface cracks may provide initiation sites for larger cracks (greater than 15m), of the type observed in Figure 5. Once the larger cracks progress to the layer of fibres closest to the surface, the cracks may progress along the fibre resin interface resulting in debonding.

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Cracks have propagated to the layer of fibres closest to the surface and disrupted the fibre-resin interface bond as evident by the cylindrical impressions on the loose pieces of resin on the surface of the laminate shown in Figure 6. The surface cracks as shown in Figure 5, would have been of sufficient depth to have propagated to the layer of fibres below and then along the fibre resin interface resulting in debonding. Although surface cracks appear to be restricted to about 15m from the surface, the surface layer has been sufficiently worn such that the cracks have reached the first layer of reinforcement. It appears that the majority of surface cracks do not progress to significant depth within the laminate verifying the finding that degradation is predominantly a surface phenomena. Startseva et al have found that mechanical properties change with depth in exposed laminates (7). McManus et al (8) have incorporated damaged material at the surface into a mechanism based model that considers degradation due to various mechanisms. Once surface cracks have progressed through the width of the degraded layer and into reinforcement, the degraded layer breaks up into smaller pieces and comes loose from the laminate, thereby exposing the fibres below to the environment without the surface layer of resin being further eroded. In this regard, degradation on epoxy 2 will progress faster than epoxy 1 as no significant cracks have been observed on the surface layer of epoxy 1. On epoxy 1, for the fibre to become exposed, the resin will have to be eroded away and premature fibre exposure caused by resin breaking free of the laminate will not occur. The 20 week exposure sampling period coincided with the end of winter therefore laminates exposed at Alkantpan may have been most affected by the exposure as this test site experienced the largest temperature range with hot days and cold nights. The thermal cycling may have induced damage within the laminate. Exposure at Irene does not appear to have as severely affected the laminate strength although the area experiences low temperatures. On average, Alkantpan is approximately 3C colder than Irene in winter. Laminates at Irene may not have been as severely affected by the exposure due to post-curing as a result of the natural radiation being approximately 23% higher at Irene when compared to Alkantpan, based on MED (Minimal Erythemal Dose) units. MED units were initially used for comparative purposes of UV radiation between exposure locations as it was readily available from the South African Weather Services and quantified UV radiation in terms of the effect it produced. The decrease in compressive strength at Durban may be due to the high humidity as Durban experiences the highest humidity of the three test sites from which laminates were sampled. The warmer winter in Durban may have facilitated post curing therefore the laminates did not lose as much strength, when compared to Alkantpan. Epoxy 2 laminates do not appear to have been affected to the same extent as epoxy 1 laminates. In contrast, laminates exposed at Alkantpan appear to not have been measurably affected. Irene and Durban have been affected to approximately the same extent and as yet the reason for this has not been established as the environments at each location experienced different temperatures, humidity and natural radiation. Conclusions regarding the strength changes may be difficult to establish after twenty weeks exposure as curing of any unreacted polymer will cause an increase in strength and offset decrease in strength due to degradation. This post curing effect is more likely in wet lay-up systems even though post curing was performed after manufacture. Due to inadequate post-curing curing in an oven, further post-curing of unreacted polymer is possible in the natural environment (9).

CONCLUSION
Glass-fibre reinforced polymer laminates have been set out for exposure in the natural environment at six different locations representing the range of climates experienced in Southern Africa. Five different polymer matrices, commonly used in industry have been selected for the exposure. Laminates are sampled bi-annually for inspection and testing. From the SEM results, it appears that the degradation progress from the surface of the laminate to the interior of the laminate. Visibly this is manifest by matrix erosion resulting in exposure of underlying fibres. Changes in strength due to degradation have not yet been established as possible post curing may result in increase in strength offsetting any decrease in strength due to degradation.
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