CONTINUOUS REINFORCED THERMOPLASTIC COMPOSITES FOR AIRCRAFT APPLICATIONS

Author: Michael Favaloro, Ticona Engineering Polymers

1. ABSTRACT: Thermoplastic composites offer substantial cost savings and improved performance as compared to thermoset parts. This paper will provide a description of properties of high temperature thermoplastic composites for aerospace applications. Matrix materials will include PPS, PEI and PEEK. A relative comparison of cost vs. performance will be provided. Limited descriptions of aerospace parts currently made in production and the manufacturing processes, will be provided. KEYWORDS: Applications Aerospace, Characterization, High Temperature Composite Materials/Structures, Flame Spread/Flammability/Smoke/Toxicity, Resins/Materials Polyetheretherketone (PEEK), Resins/Materials Polyetherketoneketone (PEKK), Resins/Materials Polyphenylene Sulfide (PPS) 2. BACKGROUND: The composites industry is undergoing substantial growth in the aerospace industry, due mainly to the fact that high performance light weight composite structures are more fuel efficient than their metallic predecessors. The current focus of the industry is on thermoset based composites, for a number of reasons. Thermoset composites have been used in the aerospace industry since the 1960s, and the design and processing knowledge to exploit the materials has developed substantially. Major investments have been made in material property databases for thermoset composite man-rated aerospace applications. In many cases these databases are treated as company proprietary intellectual property, which makes it difficult to justify investment in alternate materials and processes. Industries associated with reinforcement that utilizes thermoset-compatible sizings are mature, including weaving and conversion into prepreg. Capital equipment and support services, such as tooling and semi-automation methodologies, are well established. As expected with a maturing technology, major thermoset composite technology innovations and cost reduction opportunities are less frequent, with some notable exceptions. Aircraft designers are using more lightweight composite structures to reduce fuel consumption. However, the application of composites in aerospace is not being driven by reductions in costs for composite materials or processing. The cost reductions are coming in the form of fuel savings and not part costs.

One projected breakthrough in the composites industry cost equation is expected to involve large scale manufacture of continuous fiber thermoplastic composites. Thermoplastics offer improved raw materials and processing costs, as well as improved functional performance. This paper describes cost and performance information on three aerospace quality thermoplastic polymers used in the composites industry. 3. THERMOPLASTIC VS. THERMOSET A rational justification must be made for considering the investment into thermoplastic composites for aerospace applications. Thermoplastic matrix composites are melt processable polymers. They are heated, melted or softened, reshaped, and then cooled to a final hardened shaped. When compared to thermosets, which are cross-linked when heated and cannot be remelted or re-formed, thermoplastics provide a more tailorable and more forgiving process. Thermoplastics can be more easily re-worked and repaired. Thermoplastic raw materials have a near infinite shelf life, as compared to thermoset prepreg, with a typical shelf life of ~ 6 months, requiring refrigeration, tight schedule control of material receipt and conversion to final form. Without tight schedule control, scrap prepreg costs can become very high. Thermoplastics do not require refrigeration and storage costs are less. Thermoplastics are typically 4X tougher than the more toughened thermosets, resulting in more impact resistance and damage tolerance. The thermoplastics considered in this paper are relatively insensitive to aircraft fluids and chemical attack, and, with one exception, insensitive to moisture. Thermoplastics offer substantial reductions in flammability, smoke and toxicity performance as compared to thermosets, which is of major importance in man-rated aircraft. When considering processing of the two families of materials, a major investment of capital currently exists in the industry for thermoset composite processing. While some of the equipment, such as autoclaves, could also be used for thermoplastic processing the relatively slow and inefficient process times required for heat up and cool down of the autoclave would reduce process and cost efficiency options associated with thermoplastics. Thermoplastics are typically heated, formed and cooled rapidly as compared to thermosets, resulting in cost reduction. The use of thermoplastic processes would eliminate the need for bagging materials and labor. With the use of in-line consolidation techniques (Reference 1) kitting and debulking steps and equipment would also be eliminated. These techniques would also eliminate the need for autoclave processing, which would reduce capital cost, floor space requirements, and processing bottleneck issues. The green processing of thermoplastics vs. thermosets cannot be overstated. Thermoplastics can, by definition, be fully recycled. Little to no volatile organic compounds (VOCs) are released during processing. Process scrap can also be reduced substantially with existing fiber placement technology (Reference 2). 4. CANDIDATE THERMOPLASTICS Three aerospace grade thermoplastics are discussed in this paper. Poly ether ether ketone (PEEK) has extensive commercially available data. It is considered the baseline for aerospace grade thermoplastic composites, and has been considered and applied in the industry for over twenty years. There are several suppliers of PEEK resin in the industry

Polyetherimide (PEI) is manufactured by Sabic Innovative Plastics, formerly GE Plastics. PEI composites are used in numerous aircraft structures, including Airbus floor panels, Gulfstream rudder ribs, pressure bulkheads, and many more. Polyphenylene Sulfide (PPS) is manufactured in a high quality linear form by Fortron Industries, a joint venture owned by Ticona, a business of Celanese Corporation, and Kureha Corporation. This polymer is the lowest cost of the three thermoplastics discussed in this paper. Successful application of PPS composites in aircraft include the undercarriage door for the Fokker 50, fixed wing leading edges for the Airbus A340 and A380, keel beams and others. A comparison of candidate resins is shown in Table 1. It must be noted that the use of Tg as an upper temperature use limit is not valid for thermoplastics. PEI exhibits creep initiation well below its Tg, and as a result, has an upper temperature use limit that is similar to PPS. Furthermore, semi-crystalline thermoplastics such as PEEK and PPS are typically used under load for extended periods above their Tg. TABLE 1: Candidate Resin Comparison Resin Tg (C ) Tm (C ) Relative Resin Cost 2.7 1.3 1 Relative Processing Cost 1.2 1.4 1

PEEK PEI PPS Linear

143 210 90

343 360 285

5. COST COMPARISON
FIGURE 1: Cost Comparison of Conventional and Candidate Composites Systems

100

Processing Material

System Cost in %

80 60 40 20 0
ion al Co nv ent PE EK PE I

As described above, thermoplastic composites may exhibit substantial cost savings as compared to relevant thermosets. Table 1 shows a relative comparison of conventional thermoset composites to the three thermoplastics. This comparison is highlighted in Figure 1. When considering PEEK composites, the higher material cost is offset by lower cost conversion processing. The cost of PEI prepreg is about half the cost of PEEK prepreg, but higher processing temperatures are needed, which could result in higher processing cost. The net cost of PEI composites is still lower than PEEK composites. The lowest cost option is PPS, which has a prepreg cost of approx. 25% less than PEI, and lower processing temperatures / processing cost.

PP S

6. CHEMICAL RESISTANCE Resistance to some typical solvents and fluids is shown in the following table. (References 3, 4, 5, 6, 7) TABLE 2: Chemical Resistance of Candidate Resins PPS PEI PEEK RT 100C RT 100C RT 100C Sulfuric acid, <10% A A A C B B Sulfuric acid, >10% A C A C C C Ethanol A A A B A A Ethylene Glycol A A A B A A Acetone A A C C A A Toluene A A C C A A NOTES; A= no attack, B=slight attack, C=severe attack PPS has excellent chemical resistance. It has no known solvents below 200C. PEEK also exhibits very good relative chemical resistance with some exceptions such as sulfuric acids. PEI exhibits excellent resistance to sulfuric acids, but is susceptible to attack at higher temperatures. 7. MOISTURE RESISTANCE Water Absorption of the candidate materials is shown in Figure 2. (Reference 7) PPS exhibits the lowest moisture absorption of the three materials. PEI absorbs a substantial amount of moisture, which can result in dimensional instability and in increased creep.

FIGURE 2: Moisture Absorption of Candidate Resins

8. FLAME, SMOKE AND TOXICITY Composite material candidates for aircraft interior applications must meet stringent requirements. They must survive vertical burn flame testing, where they are exposed to a direct flame for up to 60 seconds, and rapidly self-extinguish. For this test, the number of airborne particles, number of burning particles and total burn lengths are measured. A minimum smoke density must be considered, to allow for ease of evacuation as necessary. Toxicity levels of the smoke must be low for obvious reasons. A low heat release must also be considered, to prevent spread of the flame. All three candidate materials exhibit excellent properties for use in aircraft interior applications (References 6, 7, 8). PEI and PPS are typically used in structural and non structural cabin components. PEEK is used sparingly because of the increased cost associated with the material.

9. MECHANICAL PROPERTIES In continuous fiber reinforced composites, the load carrying fibers can be utilized to address the bulk of the mechanical property requirements of an application. The matrix contributes to long term properties with toughness and long term creep resistance. Of particular concern with thermoplastic composites is creep resistance at elevated temperatures. In contrast to thermoset composite materials which exhibit decomposition at elevated temperatures, thermoplastics soften at elevated temperatures. An aircraft fuselage must survive temperature extremes without embrittlement or softening.

In a recent study at Ticona, the candidate resins, along with PEKK, were examined for long term creep resistance (Reference 9). The resins were converted to prepreg with AS4 carbon fiber by TenCate, Taunton MA., and made into test panels using an automated fabrication process by Automated Dynamics, Schenectady, NY. Testing was performed using established differential mechanical analysis methods as described in Reference 9. Test data is shown in Figure 3, PEEK and PEKK exhibit identical compliance curves, which compares
well with the Tg of the resins.

Surprisingly, the creep compliance curves of PPS and PEI also match. In this case, the substantially higher Tg of PEI does not result in improved creep performance at higher temperatures than PPS. Creep

for amorphous linear polymers is restrained only by the degree of entanglement of the larger molecules (Reference 10). Consequently, the creep compliance for the semi-crystalline PPS is identical to that for the softer, amorphous PEI.

10. SOME PPS APPLICATIONS: The fixed wing leading edge, shown in Figure 4, is made from PPS prepreg manufactured by TenCate. The prepreg layers are thermally stamped to the desired shape, machined, and welded in place. These parts were originally developed and used in production for the Airbus A340 aircraft. They are now being used on the A380 (Reference 7). Another application using PPS composites is the keel beam, as shown in Figure 5. The substitution of metal components with PPS resulted in more than 20% by weight reduction for these parts (Reference 7).

FIGURE 4: Fixed Wing Leading Edge

FIGURE 5: Keel Beam

One projected use of PPS composites is for aircraft seat frames. PPS meets the interior FST requirements, and is by far the cheapest of the candidate thermoplastics to meet these needs. Replacement of existing aluminum and glass/epoxy seat frames will offer a substantial weight reduction for this application. 11. SUMMARY The three candidate resins are finding increased use in commercial aerospace applications. The long term investment into the higher performance PEEK material has resulted in a good database and flight history of the material. PEI and PPS are both finding uses as the reduced cost of these resins becomes obvious, and long term investments continue to be made in the material databases and processes. As these resins receive more industry acceptance, the cost reduction curves for all aerospace composite materials is expected to improve.

12. REFERENCES: 1)Favaloro, M., and Hauber, D., Process and Design Considerations for the Automated Fiber Placement Process, ADC Acquisition Company, presented at the SAMPE 2007 fall technical conference, Cincinnati, OH 2) Black, Sarah, New Equipment Brings Tape Placement Within Reach of Smaller Composites Shops, High Performance Composites Magazine, Nov, 2003 3) Chemical Resistance Data, CRAFTECH Industries, Inc., Hudson, NY , www.craftechind.com 4) Victrex Chemical Resistance Data, www.victrex.com, 5) ULTEM Chemical Resistance Chart, provided by Westlake Plastics Company 6) Properties of Key Products for Aircraft Interiors Architecture for the Sky, provided by SABIC Innovative Plastics 7) Fortron PPS for Thermoplastics Composites, TICONA Engineering Polymers, www.ticona.com 8) Improved Fire- and Smoke Resistant Materials for Commercial Aircraft Interiors A Proceedings, Committee on Fire- and Smoke- Resistant Materials for Commercial Aircraft Interiors, pages 93 to 114, National Academy Press, Washington, DC, 1995 9) Ramathal, H., and Favaloro, M., A Comparison of Maximum Use Temperatures for High Performance Thermoplastic Composites, presented at the SAMPE 2008 fall technical conference, Memphis TN 10) Sepe, M. P. Dynamic Mechanical Analysis for Plastic Engineers, PDL Handbook Series, Plastic Design Library, 1998