High Performance Composites from Renewable Resources

B. M. Weager, E. L. Arnold, G. R. Bishop Composites Evolution Ltd 4A Broom Business Park, Bridge Way, Chesterfield, S41 9QG, UK

ABSTRACT Composite materials derived from natural, renewable sources have received significant interest in recent years due to increased environmental awareness, concern about the depletion of non-renewable resources and the instability in oil prices. Natural fibres, such as hemp, flax and wood, are already used as composite reinforcements, in particular in the automotive industry, to reduce weight, cost and environmental impact. However, the fibres tend to be short and randomly oriented, thus limiting the mechanical properties of the resultant composite parts. The COMBINE project, co-funded by the Technology Strategy Board, was undertaken to develop higher performance natural fibre-reinforced thermoplastic composites suitable for use in structural or semi-structural applications. Materials with significantly improved modulus and strength were obtained by improving the natural fibre extraction processes and developing continuous, aligned natural fibre yarns and fabrics suitable for composite reinforcement. These high-performance reinforcements based on flax and hemp were combined with polypropylene (PP) and polylactic acid (PLA) biopolymer using a range of novel comingling techniques. Vacuum and press moulding processes were developed and optimised for the materials and suitable joining and coating technologies were identified. A range of tests were conducted including tensile, impact and biodegradation, and the potential for recycling was assessed. Three case study parts were developed and tested, including interior and exterior automotive parts and a marine headliner panel. The materials have recently been launched commercially by Composites Evolution Ltd under the tradename Biotex and are available as yarns, fabrics and preconsolidated sheets in flax-PP, flax-PLA and 100% flax versions.

INTRODUCTION Recently there has been a dramatic increase in interest in environmentally friendly products and technologies throughout society. Biocomposites, where either the fibre or matrix, or ideally both, are derived from natural, renewable resources, have a significant role to play in the next generation of sustainable materials. These materials help reduce CO2, preserve non-renewable resources, increase sustainability and in some cases can be biodegradable or compostable. They are typically lightweight, can have low raw material cost, offer reduced

energy use/cost and, aside from the environmental benefits, can have good technical performance in their own right. Natural fibres such as hemp, flax and wood are already used in the automotive industry to reduce weight, cost and environmental impact. In fact, on a stiffness-for-weight basis, natural fibres can have equal or superior properties to glass fibres. Table 1 from [1] compares typical properties for natural fibres and glass fibres. It can be seen that natural fibres have similar modulus (stiffness) to glass fibres but approximately half the density.

Table 1. Comparison of properties of natural fibres [1]. Property Diameter (m) Density (g/cm3) Tensile modulus (GPa) Tensile strength (MPa) Elongation to failure (%) Specific tensile modulus (GPa/g/cm3) Specific tensile strength (MPa/g/cm3) Glass 10-20 2.54 72 1500 4.8 28 590 Flax 19 1.4 - 1.5 50 - 70 500 - 900 1.5 - 4 41 480 Hemp 25 1.48 30 - 60 300 - 800 2-4 30 370

Existing natural fibre composites tend to use short, randomly oriented natural fibres, which results in relatively low composite mechanical properties and therefore applications are limited to non-structural parts. It is well-known that fibres provide the highest strength and stiffness when they are continuous and aligned in the direction of applied load. Natural fibres are naturally discontinuous and conventional spun yarns tend to be highly twisted which leads to fibre misalignment and poor wet-out. Figure 1 from [2] shows that, while the dry yarn strength increases with increasing yarn twist, the resultant composite strength reduces rapidly. To date, natural fibres have mainly been used to reinforce synthetic polymers such as polypropylene and unsaturated polyester resin, so the composite system is not fully renewable. So there are significant barriers to overcome in the quest for high-performance, 100% renewable biocomposites, in particular in the area of low twist, high performance yarns and textiles and the combination of natural fibres and bio-based polymers. A UK-based consortium has been working to overcome some of these barriers, through a project, cofunded by the Technology Strategy Board, called COMBINE (www.combineproject.org.uk). This paper discusses the outputs of this project, from materials development, processing and testing to end of life options and the development of prototype case study parts. Following successful development, the materials have been launched commercially with the name Biotex and are available in Flax, commingled Flax/PP and commingled Flax/PLA versions.

700 Dry yarn 600 Impregnated yarn 500 400 300 200 100 0 0 50 100 150 200 250

Strength (MPa)

Twist (turns/m)

Figure 1. Effect of yarn twist on dry yarn strength and impregnated yarn (composite) strength. Minimum yarn strength 200MPa. Data from [2].

MATERIALS DEVELOPMENT Hemp and flax fibres were selected because they have good mechanical properties and can be grown in European climates. The fibres were improved by developing the agronomy, retting (where bacteria loosen the fibres in the crop stem) and fibre extraction processes, and investigating treatments to improve the fibre-matrix bonding. The work initially focussed on thermoplastic matrix polymers including polypropylene (PP) and polylactic acid (PLA), a biopolymer from corn starch. In particular, the effects of polymer viscosity and compatibilising additives on consolidation and fibre-matrix bonding were studied. Natural fibre yarns were developed using novel twistless spinning techniques thereby producing continuous reinforcements with straight fibres, good mechanical properties and good wet-out and impregnation. Woven fabrics were produced from the yarns in a range of weave styles designed to minimise crimp and maximise drape. Yarns and fabrics were produced from flax and hemp to be suitable for reinforcing thermosetting resins such as unsaturated polyester (UP), epoxy or bioresins. In addition, novel commingled yarns and fabrics containing blends of natural fibres (flax or hemp) and thermoplastics (PP or PLA) were developed for rapid moulding of thermoplastic biocomposites - the thermoplastic melts on heating to form the matrix of the composite. Figure 2 shows examples of the materials developed.

Figure 2. Flax-based yarn, fabric and preconsolidated sheets developed during the project.

PROCESSING & PERFORMANCE The new high-performance natural fibre reinforcements were evaluated in a range of standard composite processes. The flax fabrics were readily processed by hand lay-up and vacuum infusion, whilst the commingled natural fibre-thermoplastic materials were successfully processed by vacuum consolidation and hot press moulding. The laminates were subjected to a range of tests including tensile, flexural and impact and typical results are in summarised in Table 2.

Table 2. Typical mechanical properties of the biocomposites developed including Flax/PLA, Flax/PP and Flax/unsaturated polyester. Property 40% Flax/PLA (press moulding) Density (g/cm3) 1.34 Tensile modulus (GPa) 13.2 Tensile strength (MPa) 102 Elongation (%) 1.6 Flexural modulus (GPa) 7.8 Flexural strength (MPa) 131 Charpy impact, unnotched, 33 flatwise (kJ/m2) Charpy impact, unnotched 28 edgewise (kJ/m2) 40% Flax/PP (press moulding) 1.13 8.1 56 1.5 4.5 79 27 23 33% Flax/UP (vac infusion) 1.33 7.2 68 2.5 4 97 28 28

Figure 3 and Figure 4 show the effect of processing parameters (temperature and time at temperature) on the flexural modulus and flexural strength of Flax/PLA composites made by vacuum consolidation. It can be seen that the optimum processing temperature is approximately 190C and the optimum time at temperature is approximately 5 minutes. At lower temperatures the composite is not fully consolidated resulting in lower properties. At higher temperatures and for longer times at temperature, the properties are reduced due to thermal degradation of the natural fibres.

Figure 3. Effect of temperature and time at temperature on the flexural modulus of laminates made from 40vol% Flax/PLA using vacuum consolidation.

Figure 4. Effect of temperature and time at temperature on the flexural strength of laminates made from 40vol% Flax/PLA using vacuum consolidation.

Figure 5 shows the effect of temperature on the consolidation and degradation of Flax/PLA laminates. It can be seen that at 170C the laminate is not fully consolidated, whilst at 230C the composite is degraded. The optimum processing temperature appears to be around 190C.

170C

190C

200C

210C

230C

Figure 5. Effect of temperature on the consolidation and degradation of laminates made from 40vol% Flax/PLA using vacuum consolidation with 40 minutes dwell at temperature.

END OF LIFE OPTIONS The recyclability of the novel biocomposites has also been studied. Flax/PLA laminates were shredded, regranulated, injection moulded and tensile tested and this cycle was performed 5 times. After the first shredding and recycling operation, the aligned fibre structure was lost, so mechanical properties reduced significantly. Therefore, the recycled materials can only be used for lower grade applications. But, for subsequent cycles, the properties did not reduce significantly; the modulus was unaffected and the strength was only reduced slightly (approximately 10% per cycle) due to shortening of the natural fibres (Figure 6). It should be noted that Flax/PLA is also biodegradable and compostable in the correct conditions. This would typically be conducted in an industrial composting facility.

Figure 6. Effect of repeated shredding, regranulating and injection moulding on the tensile strength of Flax/PLA composites.

CASE STUDIES A range of prototype components (Figure 7) have been developed from the new high performance biocomposite materials including a marine headliner panel from Fairline Boats and two interior automotive parts from Jaguar and Land Rover. Flax/PP fabric was selected by Jaguar and Land Rover due to its combination of good mechanical properties and environmental credentials. Prototype door modules from both Land Rover Defender and Jaguar XF models were manufactured and their performance compared to current production parts. The biocomposite Defender Front Door Module was approximately 60% lighter than the current steel part at the same stiffness, while the Jaguar XF Rear Door Module was 35% lighter than the current glass filled PP component for the same thickness. Detailed component evaluation is currently underway.

Figure 7. Prototype parts made from the Flax/PLA biocomposites developed.

COMMERCIALISATION Following successful development, the materials have been launched commercially by Composites Evolution Ltd under the tradename Biotex (www.compositesevolution.com). The materials are backed up by 130 years of experience in spinning and weaving natural textiles and decades of experience in composite materials, processing and applications. There are currently three material options - Flax, commingled Flax/PP and commingled Flax/PLA and the formats available include yarns (125-2000tex), woven fabrics (250800gsm in a range of weave styles) and preconsolidated sheets (typically 0.8-2.8mm thick). The materials are already receiving significant interest from a host of sectors including automotive, construction, marine, sports and consumer goods.

SUMMARY & CONCLUSIONS Interest in biocomposites has increased dramatically in recent years. Existing natural fibre composites have limitations as they typically use short, randomly oriented fibres and synthetic polymers. The COMBINE collaborative project has developed a new range of

high-performance natural fibre composites using a twistless yarn technology where the fibres are kept straight to provide optimum mechanical properties and wet-out/impregnation is straightforward. The materials have been characterised using a range of process techniques and test methods. End of life options including recycling and biodegradation have been studied. A number of case study parts have been produced including automotive and marine components. Following successful development, the materials have been launched commercially under the tradename Biotex. The materials available include Flax, commingled Flax/PP and commingled Flax/PLA and the formats available include yarns, fabrics and preconsolidated sheets.

ACKNOWLEDGEMENTS These materials were developed during the Combine project, which was co-funded by the UK Technology Strategy Board's Collaborative Research and Development programme (contract no. TP/5/SUS/6/I/H0284C). The project partners were NetComposites, Queen Mary University of London, Springdale, Tilsatec, John L Brierley, Sam Weller, Millfield and Fairline.

REFERENCES 1. 2. Weager, B.M., Natural Fibre Composites, Report for Materials KTN, 2010. Goutianos, S., Peijs, T., The optimisation of flax fibre yarns for the development of high-performance natural fibre composites, Advanced Composites Letters, v 12, n 6, pp 237-241, 2003.