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Processing of Thermoplastic Composites

by William Lai

Using polymer resins as matrix for composite materials has been widely studied since the early twentieth century 1,2, and resin-based composites have been used in many industrial area including aerospace engineering, automotive engineering, electronic devices, and other general applications. The beauty of it is that polymer resins can be reinforced with glass, carbon, aramid or metal fibres for higher strength and, in the meantime, keep advantages of polymers such as lightweight, resistance to corrosion, fire, or other severe environmental conditions, and ease of machining of complicated structures. Polymer resins are classified into two categories2,3,19, thermoplastics and thermosets. Theoretically, thermoplastic is polymer that will turn into a liquid state when heated and become a brittle and glassy state when cooled sufficiently; whereas thermoset is polymer that does not have this process reversibly. Therefore, thermoplastics can be molded into a new shape and, at this point, easily recycled and reused. For thermoplastics, most of them are medium to high molecular weight polymers. Different form thermosets, there is no crosslink between polymer chains. Instead, those long molecules chains in thermoplastics held each other through weak Van der Waals forces. Comparing to thermoplastics, it is easier for thermosetting resins to be introduced into fibres at low pressures due to the very low viscosity. Thermoplastics tend to have high melt viscosities between 500 and 1000 times more than thermosets3. This makes thermosetting resins a matrix choice for most of the structural composite materials. However, because of the outstanding properties of thermoplastic resins including impact and damage resistance, as well as the unlimited shelf life, short processing time, and the ability to be readily recycled2,4, they are still being considered as matrix materials in many applications. Amount all of the thermoplastics, polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyetherimide (PEI), and polyetherether ketone (PEEK) are some of the most commonly used resins in thermoplastic composites. 1

Polymer and Composites Processing

Generally speaking, processing of thermoplastic composites can be discussed in three folds1,4,8,10,18,19: prepreg, forming, and joining. The first fold, prepreg, is focusing on techniques of the formation of matrix-fibre (reinforcement) combinations. The second fold, forming, is about techniques of how to process materials into desired shape. And the final fold, joining, is the welding related process that bonds composite blocks together. In this chapter, different processing methods will be introduced based on these three areas.

10.1 Prepreg
Thermoplastic prepregs are products contained matrix and fibres combination. Several different methods can be employed to accomplish the thermoplastic prepregs. Not like thermosets, thermoplastics tend to have much higher melting viscosities. It is more challenging to introduce thermoplastic resins into fibres. As a result, wetting between fibres and matrix is more difficult. It has been studied that a proper choice (which depend on both fibre and matrix types) of fibre treatments, including cleaning, etching, or oxidation is able to enhance the adhesion through the provided sites for adequate bonding. After fibre treatments, the next step is wetting, which is for the fabricating thermoplastic prepregs. These thermoplastic prepregs are basically rigid matrix-fibre combinations and one-step-away from finished state of composites. Several methods have been reported to accomplish this step and will be briefly introduced in the following paragraphs. 10.1.1 Hot Melt Coating Hot melt coating is one of the most commonly used and easiest processes for forming matrix-fibre combinations. The simplest processing flow is shown in
figure 11,4,5. The idea of this technique is to lower down viscosity of resins by melting them. At the beginning, unwounded fibre tows are prepared for using.

They are being spread by using rollers, air jets, or other methods to increase the contact surface area with resins later. The spread fibres are fed into a die in which the combination is taken place. Resins as matrix can be in either melting polymer form or coated on release papers. Applied pressure and heat are employed at this stage for combining resins and fibres. Although high temperature can melt the resins and reduce their viscosity, it may also decompose and weaken the resins. As discussed above, there is no solvent requirement in any of the steps while employing this method.

Processing of Thermoplastic Composites

Figure 1. Process of hot melt coating.4 10.1.2 Solution Processing As the name said, solution processing is a technique of combining matrix and fibres by dissolving resin and wet fibre in with solution1,4,5,6. As mentioned, thermoplastics have trouble of introducing with fibres due to their much higher viscosity. By dissolving resin into solution, viscosity of thermoplastic polymers can be reduced and, therefore, ease the impregnation. There are couple important issues that have to be considered when using solution processing related to the employed solution. A suitable solution is required not only to dissolve but also not to destroy the polymer structure. In addition, solvent may be highly toxic and residual solvent also affect the propertied of final composites. Thus, it is a difficult task and challenge need to be considered to fully remove all the solvent from the thermoplastic prepregs. 10.1.3 In-situ Polymerization In-situ polymerization1,4,5,6 requires using fibre and monomers or prepolymers. They are all put together in solution for chemical reaction of polymerization. Only certain of limited types of thermoplastics, for example some of the PAs, are suitable for this process. Unfortunately this process has long curing-period requirement and the co-exiting products such as solution evaporation and water or other compounds yielded through the chemical reaction during the curing/ post-curing processing may also need extra attention to take care of. 10.1.4 Film Stacking Film stacking method1,5 is basically stacked up layers of fibres which are usually in tape form and layers of thermoplastics. The stacked films will be fully combined and yield high quality of combining matrix-fibre laminates after consolidation in high temperature and pressure condition. This

Polymer and Composites Processing

technique can be considered as improvemed one from the hot melt coating technique that lower temperature is required. However, longer processing time period may be asked for resins to uniformly flow and fully wet the fibres. 10.1.5 Powder Coating Powder coating is using powder form of polymers with fires to construct the prepregs. A brief processing flow is illustrated and shown in figure 2. This method requires very well-spread fibres in order to accomplish wetting process. Usually powders with diameter of 2 to 50 micrometer are used1,4. Powders are charged and fluidized and carried by air. When powders contact fibres, they are electrostatically deposited. After coating, the powder treated fibres can be directly rolled up as finished prepregs or they can be employed heating treatment in oven and then cooled as another type of finished prepregs and ready for future lay-up and forming process. In order to prevent powders from removal, water is sometimes spread on the prepregs before handling4. Powder coating is especially a very good solution for dealing with thermoplastics with very high viscosity or low solubility. However, during the step of powder spraying, there is chance that powder will harm and break fibres. In addition, it is difficult to control the amount of resins. Too much of resins may decrease mechincal properties of the composites.

Figure 2. Process of powder coating.4,7

Processing of Thermoplastic Composites

10.1.6 Commingled Fiber In this technique, continuous long fiber form of thermoplastic resins is being used1,5. They are mixed with the reinforcement fibres for mixing fibre bundles. When the mixing fibre bundles are heated to the melting point of the resins, thermoplastic will be melt and cover up reinforcement fibres. The temperature requirement in commingled fiber technique is not as high as other techniques. Another advantage of this method is that the matrix/reinforcement composition can be controlled highly accurate by using this method. In addition, the products are softer and more suitable for applying on mold with more complicated structure.

10.2 Forming
Forming is the process that uses pressure and heat to make flat sheets or stacked-up plys of prepregs into laminates and then process them into desired shapes. Generally, thermoplastic composites processing is fast and the products are readily recyclable. Besides, raw materials have unlimited shelf life and do not need low temperature for storage3. Prepregs can be obtained by one of the techniques discussed in section 10.1. They have will be laid-up and undergone a sequence of processes with pressure and thermal treatments involved. The fundamental of the processing sequence includes three major steps: melting, consolidation, and solidification4,8,9. Figure 3 shows a brief illustration by plotting them in time profile 9,10. First, heat is applied to increase temperature above its melting point (Tm). Typically, the heating process is done in external oven which uses infrared radiation as heating sources. Mold may sometimes provide heat for melting as well. The heating time will depend on the using forming techniques. During this step, low pressure can be applied if needed. Next, pressure is applied while remaining the temperature achieved in the prior step. This step is called the consolidation step which is for removing voids and forming interface bonding. The requiring pressure is usually about 1 MPa8. The consolidation time is highly depending on product type, form, or shape of the using prepregs. Finally, the composites are cooled. Applied pressure will be removed after the temperature drops below the glass transition temperature (Tg). The cooling time will be depending on the processing methods. The cooling rate is also important as it will influence the crystalline structure of composite and, in this way, having effects on mechanical properties of accomplished products. Following the basic concept, several techniques have been shown to practice the process the forming sequence.

Polymer and Composites Processing

Figure 3. Pressure-Temperature-Time Profile for consolidation.9 There are two modeling assumptions for consolidation 11: isothermal consolidation and non-isothermal consolidation. Isothermal consolidation means all polymers under the same temperature, whereas non-isothermal consolidation means temperature varies through thickness. Theres an additional issue that we should be aware when using thermoplastics. It has been shown that thermoplastic products will be undergone deconsolidation if using them in heating environment 12. Moreover, experimental results show deconsolidation occurring even polymers were consolidated during processing. 10.2.1 Matching Die Press Forming This is a widely available method that has a very direct processing concept: pressing raw materials with top and bottom of matching dies with designed structure shape4,9,13. Consolidation will be done during the process when heat and pressure are applied. After that, the composite can be cooled rapidly to obtain the finished product. Usually harder material such as metal is used for female part of the matching die and softer material like rubber is used for the other part of the matching die. The advantages of this method are that it has comparably higher heating and cooling speed without additional sealing sheets or vacuum bags and it is simple and easy to

Processing of Thermoplastic Composites

manufacture. However, the heating done by this method is relatively less uniform. 10.2.2 Hydroforming Following by the basic concept of press forming, this method uses hydraulic pressure to obtain the target shape4,8,9. Usually a flexible rubber is used on the one side of mold and a hydraulic system is used on the other side. With different designs, hydraulic pressure can be used for either male or female side of the mold depends on the other side is concave or convex. 10.2.4 Autoclave Forming This process is a very suitable option for complex configuration8,9. Unconsolidated sheet are place on the surface of mold. Vacuum bags are used to seal the entire structure in order to use atmosphere pressure for pressing. Vacuum process is used to remove water, air, and any evaporated chemical solution as well as letting laminates fully attach on mold surface. Typically, this method is having comparably lower heating and cooling speed result in longer production time. Besides, it requires higher level of skill to manipulation. However, the heating done by this method is relatively more uniform. 10.2.4 Diaphragm Forming In this process, unconsolidated prepreg sheet and of sheets of diaphragms are stacked with edges fixed and undergo the whole process in autoclave4,8,9. The external air pressure is applied to force the sheet stack (unconsolidated sheet sandwiched by diaphragms) fully attach the desired surface shape which is the mold designed and prepared at the bottom. This technique provides great structural properties due to continuous fibres used and it is good for complex structure. Setbacks of using this method are that only constant thickness of product is able to get and it needs to keep fibre distribution uniformly. It is illustrated in figure 4.

Polymer and Composites Processing

Figure 4. Diaphragm forming.

10.3 Joining
Joining means combining two or more blocks of composite materials together and making a continuous structure. The beauty of thermoplastic composites compare to thermoset composites is that many options of joining techniques can be employed. These joining techniques can be classified into three categories including mechanical fastening, adhesive bonding, and fusion bonding or welding4,8,9. Mechanical fastening and adhesive bonding are general options which are similar to thermoset composites. Typically, mechanical fastening involves hole drilling and additional bolts inserting. This method is straight forward. The strength of joints is almost guaranteed and easy to analyze. However, the drilled holes may cause weakening and create local stress concentration. The excessive creeping was suspected on thermoplastics at first but has been proved having similar response on thermoplastics as on thermosets and no need to be conferenced. On the other hand, adhesive bonding involves adhesives added in between parts. The mechanical properties are more uniform compared to mechanical fastening as there is no geometry local discontinuity. Although the concept of adhesive bonding on thermoplastics is similar as on thermosets, not always the same chemical compounds can be effectively used. Searching for right adhesives is a broad and important study for using adhesive bonding on thermoplastic composites. Welding is the joining technique particular for thermoplastic composites because of the feature their ability to be re-melted. It melts adhesives as inter-materials. Not only does it provide a more uniform surface mechanical property similar to adhesive bonding but also can it possibly have better compatibly since the same thermoplastic can be used as the one used in

Processing of Thermoplastic Composites

resins. Weld strength 14 is determined by specimens broken under torsional and compressional loads. The strength depends on energy input and degree of material flowing out of the interface region. There are many welding techniques and will be introduced in following sections. 10.3.1 Flat Melt Fusion This method is straight forward that heated tool is placed on the desired welding surface of the block to melt its matrix. An additional layer of resin without any fibre inside can be used for welding. Pressure is added to compress blocks together with the melted area/layer working as joining. 10.3.2 Dual Resin Bonding Similar to the flat melt fusion method, an additional welding layer is used in dual resin bonding method. However, instead of using the same material in matrix, another thermoplastic with lower melting temperature as the welding layer is employed this method. For example, it has been shown using PEI layer for PEEK based reinforced laminates welding8. The advantage of this method is that the possible damages which may be done on welding blocks can be easily avoided since the welding temperature is not high enough to melt the matrix in target blocks. 10.3.3 Resistance welding
In Resistance welding, resistive elements (usually metallic are embedded in thermoplastic film and sandwiched between laminate parts. Resistance here is used to generate heat to melt the matrix of the film for welding. Metal mesh used as alternative heating element for the joining in order to get homogeneous temperature distribution for better bonding between matrix and metal mesh. It can be examined through fracture tests 15. This technique is simple, fast, and low cost4.

10.3.4 Induction welding Induction welding is the application of eddy current4,8,9. Similar to resistance welding, induction coil is used under an applied electromagnetic field to generate heat through corresponding eddy current. One of the drawbacks of these two film-adding methods is that the additional materials may affect the composite such as reducing the strength if they are not compatible with thermoplastic resins. 10.3.5 Ultrasonic welding Ultrasonic welding is a widely used commercial technique with quite a large amount of research. Blocks pending to weld are placed and compressed in

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Polymer and Composites Processing

the device. Ultrasonic horn8,9 is used to provide ultrasonic vibration which is usually greater than 20 kHz8. The ultrasonic vibration will convert and generate hear. If the block surface is not smooth, energy direction (as shown in figure 5) may be observed. This special characteristic can be used to localize target area being melted and undergoes welding. In studies, simulation and experimental results16 both show that initial heat start the welding process is from interfacial friction rather than viscoelastic heat. But after glass transition temperature, viscoelastic heating becomes dominant. Rate of heating at the interface is greatest at the beginning of the weld cycle. It then significantly slows down after the interface temperature reaches 250C14. The temperature at interface reaches peak before the weld is completed within body increase most rapidly at temperatures near the glass transition temperature.

Figure 5. Typical configuration of parts in ultrasonic welding. 17

10.4 Conclusion
Due to much higher of melt viscosities, processing of thermoplastic composites is more challenging than thermoset composites. However, the uniqueness of thermoplastics still makes a huge room for their application. Processing methods are discussed in three folds of in this section including prepreg, forming, and joining. Process prepreg is for helping combination of resins and fibres. It is a special and important research area for thermoplastic composites. Forming techniques are the processes of fabricating materials into desired shape, 2D or 3D. Joining is the process that bonds composite blocks together. Beside general joining technique similar to thermoset composites such as mechanical fastening, adhesive bonding, welding related methods are those make thermoplastic composites unique. They are useful methods particularly thermoplastic composites.

Processing of Thermoplastic Composites 11

References
1. National Materials Advisory Board, The place for Thermoplastic composites in structural components, National Research Council, U.S.A., 1987 2. L Mascia, Theroplastics: Materials Engineering, Applied Science Publishers Ltd., England, 1982. 3. H F Mark, N Bikales, C G Overberger, G Menges, and J I Kroschwitz edited, Encyclopedia of polymer Science and Engineering, John Wiley and Sons Inc., vol.4, 1985. 4. S Beland, High Performance Thermoplastic Resins and Their composites, National Data Corporation, 1990. 5. J B Cattanach, G Guff, and F N Cogswell, The processing of Thermoplastics Containing High Loadings of Long and Continuous Reiforcing Fibers, Journal of Ploymer Engineering, vol. 6, no. 1-5, pp. 345-362, 1986. 6. J D Muzzy, Processing of Advanced Thermoplastic Composites, The Manufacturing Science of Composites, vol. 4, pp. 27-39, 1988. 7. J Muzzy, B Varughese, V Thammongkol, and W Tincher, Electrostactic Prepregging of Thermoplastic Matrices, SAMPE Journal, vol. 25, no. 5, pp. 15-21, 1989. 8. F C Campbell, Structural Composite Materials, ASM International, 2010. 9. D A McCarville and H A Schaefer, Processing and Joining of Thermoplastic Composites, ASM Handbook, vol. 21, ASM International, 2001. 10. J Muzzy, L Norpoth, and B Varughese, Chracterization of Thermoplastic Compisite for processing, SAMPE J. vol. 25, no.1, pp. 23-29, 1989. 11. K Friedrich, S Fakirov, and Z Zhang, Polymer composites from nanoto macro scale, Springer, 2005. 12. F Henninger, L Ye, K Friedrich, Deconsolidation Behavior of Glass Fibre Polyamide 12 Composite Sheet Material During Post-porcessing, Plastic, Rubber and Composites and Applications 27, 287, 1998 13. S K Mazumdar, Composites Manufacturing: materials, product, and process, CRC Press, 2002. 14. M N Tolunay, P R Dawson, K K Wang, Heating and Bonding Mechanisms in Utrasonic Welding of Thermoplastics, Polymer Engineering & Science, vol23, no.13, pp. 726733, 1983.

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Polymer and Composites Processing

15. M Hou, M Yang, A Beehag, Y W Mai, L Ye, Resistance welding of carbon fibre reinforced thermoplastic composite using alternative heating element, Composite Structures, vol. 47, no.14, pp. 667672, 1999. 16. 16. Z Zhang, X Wang, Y Luo, Z Zhang, and L Wang, Study on Heating Process of Ultrasonic Welding for Thermoplastics, Journal of Thermoplastic Composite Materials, 2009. 17. A Benatar, Joining of Polymetric Composites, The Manufacturing Science of Composites, vol. 4, pp. 141-153, 1988 18. Daniel M Maguire, Joining thermoplastic composites, SAMPE Journal, vol. 25, no. 1, pp. 11-14, 1989 19. S Beland, High Performance Thermoplastic Resins and Their composites, National Data Corporation, 1990.