THERMOPLASTIC RESINS

Lars A.Berglund

posites offer advantages. They have very low Thermoplastic composites form a fairly new toxicity since they do not contain reactive group of materials. Commercial prepreg tape chemicals (therefore storage life is infinite). such as CF/PEEK (carbon fiber/polyether Because it is possible to remelt and dissolve etherketone) and later CF/PPS (polyphenyle- such thermoplastics, their composites are also nesulfide) was introduced in the early 1980s. easily recycled or combined with other recyHowever, as early as 1966, Menges reported on cled materials in the market for molding improved static strength and fatigue resistance compounds. In the aerospace market, composites based when epoxy was replaced by polyamide 6 as on toughened epoxies dominate. The potena composite matrix (Menges, 1966).In the mid tially cheaper manufacturing of thermoplastic 1970s there was interest in CF/PSU (Po1YSu1- composites has not yet been realized to the fone) due to expectations of better processing methods and improved toughness characteris- extent necessary to motivate large-scale investtics. However, solvent resistance was found to ment in new manufacturing equipment. be a problem. Composites later introduced However, for the next generation of aircraft, based on semi-crystalline thermoplastics, such interest in thermoplastic composites is high. as PEEK and PPS, which have been introduced Higher flying speeds require higher temperatures in the materials than the maximum more recently, have excellent chemical resistemperature available from epoxy-based comtance and are superior to epoxy-based posites in use today. Since the release of gases composites in this respect. Enthusiasm for thermoplastic composites is during processing and inherent brittleness are serious disadvantages of thermoset polyimides, generated for, basically, three different reasons. First, processing can be faster than for thermoplastic composites are of great interest. In the automotive market, thermoplastic thermoset composites since no curing reaction composites are used extensively. Matched-die is required. Thermoplastic composites only compression molding of glass mat thermorequire heating, shaping and cooling. plastics (GMT), primarily based on glass Secondly, the properties are attractive, in particular, high delamination resistance and fiber/polypropylene (GF/PP), is common, because it permits fast processing cycles for damage tolerance, low moisture absorption fairly large components. In the established and the excellent chemical resistance of semifield of injection molded components, matericrystalline polymers. Thirdly, in light of als are used with long fibers (5-10mm) in environmental concerns, thermoplastic commolding pellets. This leads to improved mechanical properties compared with materi; als based 0 shorter fibeis (Truckenmueller Handbook of Composites.Edited by S.T. Peters. Published and 1991). in 1998 by Chapman &Hall, London. ISBN 0 412 54020 7

6.1 INTRODUCTION

116 Thermoplastic resins

6.2 MANUFACTURING METHODS

The principles for thermoplastic composites processing are very different from those for thermoset composites. During the processing of thermosets, the polymer is initially a liquid which then solidifies due to the formation of a three-dimensional molecular network from chemical reactions. Thermoplastics are in the solid state before processing because of their high molecular weight. They are heated above their softening temperature during
-

processing, for conversion into a high-viscosity melt. Shaping then takes place and the material solidifies on cooling. In Table 6.1, different manufacturing methods used for thermoplastic composites are outlined. Further discussion of thermoplastic composites processing is available in Chapter 24 of this book and in previous reviews (Carlsson 1991; Cogswell, 1992; Kausch, 1993). As with thermoset composites, materials with low fiber volume fractions show ease of

Table 6.1 Manufacturing routes for composites based on thermoplastic resins

Manufact zi ring ro ii te
Open mold processes 1. Autoclave

Outline of fabrication and processing methods

Unidirectional or woven fibers pre-impregnated by the resin (prepreg) are used. Other forms of prepreg have reinforcing fibers in combination with the resin as fibers or as powder. The prepreg layers are stacked on the mold surface and covered with a flexible bag. Consolidation is obtained by external pressure applied in an autoclave at elevated temperature. Prepreg tape or tape with the resin as fibers or powder are wound onto a mandrel at pre-determined angles. Heat and pressure are applied to the tape in order to continuously weld it onto the underlying material. Preconsolidated sheets are heated. Simple fixtures are then used to shape the sheets into the desired geometry.

2. Filament winding
3. Folding

Closed mold processes A mixture of molten thermoplastic and short fibers is injected into a colder 4. Injection molding (short fibers, 0.1-10 mm) metal mold at very high pressure. The component is allowed to solidify and is automatically ejected. Semi-finished sheets of glass mat thermoplastics are heated and placed in 5. Compression molding the lower part of the mold in a fast press. The press is quickly closed and (short fibers, 5-50 mm) pressure is applied so that the material can flow to fill the mold. Technology is also available where the hot molding compound reaches the mold from an extruder. The same principle as for short fiber materials. 6. Compression molding Continuous fibers require special clamping fixtures for the sheets and can (continuous fibers) primarily be used for simple geometries. A stack of prepreg is placed inbetween two diaphragms (superplastic 7. Diaphragm forming aluminium or polymer film). The diaphragms are fixed whereas the prepreg can move freely. The material is slowly deformed by external pressure and the mold. Prepreg tape or tape with the resin as fibers or powder is pulled through 8. Pultrusion a heated die to form beams or similar continuous structures with constant cross-section geometry. The material is allowed to cool and solidify. Dry reinforcing fibers are placed in the mold. Monomers and/or low 9. Resin injection molecular weight polymer with low viscosity are injected, the reinforcement is impregnated. Polymerization to a high molecular weight thermoplastic occurs by mixing of reactive components and/or thermal activation.

Material forms
processing but low stiffness and strength. On the other hand, materials with high fiber content have high stiffness and strength but require slow processing and are difficult to shape into geometrically complicated structures. For high fiber content materials, the high viscosity of a molten thermoplastic usually requires some kind of prepreg fabrication step before final processing. The prepregs may need to be combined into the consolidated, semi-finished sheets before the final processing step. Regular autoclave processing can be used for thermoplastic composites. For most highperformance thermoplastics, however, temperatures have to be higher than the typical 177C used for epoxy-based composites. Often, the composite manufacturer must purchase a new autoclave if this is the preferred processing route. Autoclave processing of thermoplastics has been modeled (Lee and Springer, 1987). Consolidation of the prepreg layers is an important issue. At a given temperature, sufficient time must be available for the polymer molecules to diffuse from one prepreg layer into the other and form strong physical entanglements (Howes, Loos and Hinkley, 1989). In addition, the air initially present in the material must be displaced. For thermoplastic composites, filament winding has demonstrated good economic potential (Egerton and Gruber, 1988). The major problem is in the welding of filaments or the tape onto the underlying composite layers. Heat has been applied by means of a gas flame, IR, laser beam or simply from a hot metal surface. Pultrusion of thermoplastic composites offers potential for faster processing than with thermoset composites (Astrom, Larsson and Pipes, 1991), due to the absence of exothermal heat generation from chemical reactions. Profiles may also be produced by roll-forming techniques similar to those used in metalworking. The shape of existing profiles can be changed. The low-cost folding technique (GE Plastics, 1990) has been used commercially by Fokker and TenCate in Holland for quite large components of fairly simple geometry.

117

Compression molding of glass mat thermoplastics (GMT) is a wide-spread process of great sigruficance in the automotive industry (Berglund and Ericson, 1994).Resin injection of polymerizing prepolymer molecules of low viscosity is in principle the same process as for thermosets although the chemical reactions lead to increased molecular weight rather than to cross-linking. Such a process does not provide the advantages of infinite storage life materials with low toxicity. Diaphragm forming is a processing route where the problem of low extensibility of prepreg-based materials is addressed (Mallon, OBradaigh and Pipes, 1989).
6.3 MATERIAL FORMS

Thermoplastic composites are usually supplied as semi-finished materials, with the exception of resin injection materials. In Table 6.2, material forms for thermoplastic composites are presented. Prepregs of high fiber volume fractions (V, = 0.6) may be prepared by solvent-, melt-, prepolymer- or powderimpregnation of the reinforcing fibers. Solvent-impregnation is limited to amorphous resins with high solubility. Melt-impregnation is a technique successfully developed by IC1 (Cogswell, Hezzell and Williams, 1981) producing high-quality prepreg. The resulting prepreg is considered too stiff, for some processing situations with little drapability in comparison with CF/EP (epoxy) prepreg. This problem is addressed in prepolymer- and powder-impregnated prepreg. One example is the FIT-technology where small tubes containing reinforcing fibers and polymer powder are used (Thiede-Smet, 1989). In addition, commingled weaves (prepregs) are available. The resin is present in the form of fibers which are melted during processing to form a matrix. Composites produced from commingled material forms may have a fairly inhomogeneous distribution of fibers (Olson, 1990). Film-stacking is a simple method often used for preparation of laboratory samples

118 Thermoplastic resins

Table 6.2 Material forms for composites based on thermoplastic resins

Material forms
Prepregs 1. Solvent impregnated

Outline of preparation procedure

Reinforcing fibers are impregnated by a mixture of solvent and thermoplastic. The solvent is removed by evaporation. Reinforcing fibers are impregnated by thin molten films to which pressure 2. Melt impregnated is applied. 3. Prepolymer impregnated Low viscosity prepolymers are used to impregnate the fibers. Polymerization to high molecular weight thermoplastic takes place during processing. Fibers are enclosed by thermoplastic powder, either in small tubes 4. Powder impregnated containing reinforcing fibers and powder or by powder particles adhering to the fibers from partial melting in a fluidized bed.
Other material forms 5. Film stacked composites Stacks with alternating layers of dry fibers and polymer film are heated and compressed. 6. Fiber hybridized weaves Roving of commingled reinforcing fibers and the matrix in fiber form. Weaves are produced from the roving. and roving Reinforcing weaves are impregnated by prepolymer liquid and 7. Prepolymer liquid and polymerized to a thermoplastic composite. dry reinforcement 8. Semi-finished glass mats Supplied as sheets prepared in belt press by extrusion and melting of films which impregnate fiber mats. Porous sheets are produced from slurry (low fiber content) of fibers and thermoplastic powder in water, by technology similar to manufacturing of paper. Recycled material can be used. Often prepared by pultrusion of unidirectional fibers and matrix 9. Pellets followed by chopping into pellets. Used in injection molding or in (low fiber content) plasticizing and/or compounding unit combined with compression moulding. Recycled material is easily incorporated.

(Hartness, 1982) although the technique has also been used commercially. In the category of materials with low fiber volume fraction (V,=: 0.2), semi-finished sheets of GMT-materials are available. They usually have random, chopped or continuous fiber mat reinforcements. Unidirectional prepreg may be used in order to selectively provide additional stiffness, strength a n d creep resistance. A n interesting step forward is provided by extrusion compounded GMT (Composite Products Inc, 1994; Hoechst AG, 1994). No semi-finished sheets are used, instead a special extruder is used to produce a hot, soft 'cake' constituted of chopped fibers and the polymer matrix, often PP. The cake is placed in a press and molded. The investment in technology is higher than for conventional GMT molding.

On the other hand, the material cost and energy consumption is reduced, greater freedom in materials selection is obtained and recycling is facilitated. Suppliers of thermoplastic composites are listed in Table 6.3.
6.4 THERMOPLASTIC RESINS

Thermoplastics have either amorphous or semi-crystalline structure (Sperling, 1992). The large, chain-like polymer molecules do not show long-range order in amorphous thermoplastics, which may be viewed as polymer glasses and, in the absence of color pigments, are usually transparent. Thermosets are also amorphous. In contrast, crystalline polymers have regions of molecular order. In meltprocessed crystalline polymers, a spherical

Thermoplastic resins 119

Table 6.3 Suppliers of thermoplastic composites

Supplier
Ba ycomp Burlington, Ontario, Canada CYTEC, Anaheim CA, USA DuPont de Nemours Bad Homburg, Germany and Newark, DE, USA

Materials
Unidirectional tapes. Matrices PP, HDPE, PA12 PC, PEI, PBT, PES, PPS, PEEK, ABS, PPO. Fibers: glass, carbon, aramid and stainless steel. Commingled yams. Carbon fiber with PEEK, PEKEKK, PA6,6, TPI (Aurum@). GF/PA6,6. Prepreg based on Avimid@K, thermoplastic polyimide, and carbon fiber. Sheets laminated of continuous fiber thermoplastic composites or unidirectional discontinuous fibers. Molding compounds of lower fiber content. Matrices: PA6,6, PEKK, PET and others. Fibers: carbon, glass and aramid. Prepreg fabrication by deposition of polymers in powder form on tow and fabrics. Wide variety of resins and fibers. GMT-materials based on glass fiber mats and PP, PBT, PC and blends PC/PBT. Unidirectional GF/PP. Unidirectional prepreg of GF/PP, GF/PA6, GF/PE, CF/PPS, CF/PA6. Pellets > 12 mm for use in plasticating extruder combined with compression moulding. GF/PA12 fabric prepreg. APC-2 (CF/PEEK) prepreg tape and tow and developmental materials, primarily for high-temperature applications. FIT-weaves (Thiede-Smet, 1989).Matrices PA12, PEI, PEEK. Glass and carbon fibers. Enichem, Milano, Italy reportedly produces GF/PP, PET, PBT with FIT-technology. Prepreg fabrics and unidirectional tape, consolidated sheets. Matrices PA6,6, PMMA, PEI, PPS and PEEK. Carbon, glass and aramid fibers. Spun yarns combining reinforcing and matrix fibers for subsequent weaving. Matrices PP, PA6, PA6,6, PPS, PC, PEI, PEEK. Carbon, glass and aramid fibers. Glass mat thermoplastic sheets based on GF/PP. Prepreg fabrics and unidirectional tape, consolidated sheets. Matrices PES, PEI and PA12. Carbon, glass and aramid fibers.

Electrostatic Technology Branford, C, USA GE Plastics Amsterdam, Netherlands and Pittsfield, MA, USA Hoechst Frankfurt, Germany Huls Marl, Germany ICI/Fiberite Monchengladbach, Germany and Laguna Hills, CA, USA Porcher Textile Lyon, France Quadrax Corp Portsmouth, RI,USA Schappe Techniques Charnoz, France Symalit AG Lenzburg, Schweiz TenCate Advanced Composites Nijverdal, Netherlands and Fountain Valley, CA, USA

120 Thermoplastic resins morphology, termed spherulitic, is often observed (Bassett, 1981). Crystalline lamellae are present within the spherulites although disordered regions exist between and within the lamellae. This is because the large size of polymer molecules inhibits perfect crystallization. The crystalline thermoplastics are therefore more correctly described as semicrystalline, since the degree of crystallinity never reaches 100%. Semi-crystalline thermoplastics can be viewed as two-phase materials with a crystalline and an amorphous phase. To illustrate the difference in behavior of semi-crystalline and amorphous thermoplastics, polyethylene terephthalate (PET),may be used as an example. PET is a thermoplastic polyester which crystallizes fairly slowly. Therefore, upon rapid cooling from the molten state, crystallization can be suppressed and an amorphous polymer is obtained (similar behaviour is shown by PEEK). Samples of PET with different degrees of crystallinity can be produced by changing the conditions of cooling. The shear modulus G' (obtained from dynamic mechanical thermal analysis, DMTA) is plotted against temperature for such samples in Fig. 6.1. The amorphous sample shows a dramatic drop in modulus at the Tg (glass transition temperature). The drop in modulus for semi-crystalline samples is less dramatic: the higher the crystallinity, the slower the drop. Above T,, material modulus is maintained by the crystalline phase (although strength usually decreases dramatically). Another effect of reduced degree of crystallinity is reduced chemical resistance. A disadvantage with semi-crystalline polymers is the high processing temperature, see Tables 6.4 and 6.5, compared with the heat deflection temperature (see next section, Table 6.11). The melting temperature, Tm,of the crystalline phase must be exceeded during processing, although the maximum use temperature, as for amorphous polymers, is still below T,. Characteristic temperatures of thermoplastics used in applications where only moderate temperatures are experienced are presented in Table 6.4. These materials are available from many different chemical companies, therefore trade names and suppliers are not listed. In Table 6.5, thermoplastics for applications at higher temperatures are listed. These polymers

I I

50

100

150 Temperature ("C)

200

250

Fig. 6.1 Shear modulus (G') compared with temperature for PET of different degrees of crystallinity.

Thermoplastic resins
Table 6.4 Characteristic temperatures for thermoplastic resins with T,< 90C

121

Polymer type Polyolefin

Polyamides

___

Chemical name
~

Structure
-

T ("C)
-10

T,,,
( "C)

Processing temp. ("C)

200-240 270-320 220-260

___

Polypropylene

Crystalline Crystalline Crystalline

165 265 180

(PP)
Polyamide 6,6 (pA6,6) Polyamide 12 (PA12) Polyethylene terephthalate (PET) Polybutylene terephthalate (PBT) 55 35

Polyesters

Crystalline Crystalline

70 20

265 240

280-310 260-290

Table 6.5 Characteristic temperatures for thermoplastic resins with T, 290C

Polymer fYPe Polyester

Polyarylene ether or sulfide
~~

Chemical name
~~ ~~

Trade name and supplier

Lexan, GE Makrolon, Bayer Ryton, Phillips PAS-2, Phillips Victrex PEEK, IC1 Hostatec, Hoechst Declar, DuPont Ultrapek, BASF Victrex HTX, IC1 Udel P1700, Amoco Victrex 4100G, IC1 Ultrason E, BASF Torlon C, Amoco Torlon AIX-159 Amoco

Structure
Amorphous crystalline Amorphous Crystalline Crystalline Crystalline Crystalline Crystalline Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous Crystalline

T,
("Ci 150 90 215 143 165 155 175 205 190 220 275 290 217 250 260 none 280 none 343 365 340 375 385 none none none none none none 390

Processing temp. ("C)

280-330 300-340 330 380400 390-415 380400 400420 420430 300-350 300-320 350400 350400 335420 340-360 400420

Polycarbonate (PC) Polyphenylene sulfide (PPS) Polyarylene sulfide PEEK PEEKK PEKK PEKEKK Polyketone Polysulphone (PSU) Polyethersulfone (PES) Polyamideimide (PAI)

Polysulfones

Polyamideimides Polyimides

Polyetherimide Ultem, GE (PW Polyimide (TPI) Avimid KIII, Du Pont Polyimide (TPI) Aurum, Mitsui Toatsu

122 Thermoplastic resins are more expensive and are often termed highperformance resins. The higher cost of these materials is due to small material volumes, more expensive monomers and more difficult polymerization procedures. Many resins used in injection molding are so called blends, physical mixtures between two thermoplastics. In the field of commercial composite materials, this technology is primarily used for GMT-materials, where composites based on PC/PBT blends are available (Table 6.3). However, for high-performance resins, blending amorphous with semi-crystalline thermoplastics is an interesting route to improved chemical resistance. Most polymer mixtures form immiscible twophase structures although PEEK and PEI may be mixed to form a miscible blend (Crevecoeur and Groeninckx, 1992). of static mechanical properties of the resins is given in Table 6.6. Resins with low Tg,such as PP and PA12, have lower modulus and strength. Their fracture toughness is high and valid data according to linear elastic fracture mechanics are difficult to obtain. Among polymers with T, well above room temperature, the modulus is fairly similar. It is controlled by weak physical forces between the molecules. Viscoelastic effects such as creep and stress relaxation during loading will affect the data. Tensile strength varies more widely than modulus between different resins. As a material property it is unfortunately not very reliable. It is sensitive to loading rate, specimen geometry, specimen preparation and the presence of microscopic flaws on the specimen surface. In addition, uniaxial resin tensile strength is different from resin strength in the composite where the stress state is different. Thermoplastics have higher fracture toughness 6.5 PROPERTIES AND DESIGN than epoxy and other thermosets, although CONSIDERATIONS epoxy fracture toughness can be improved by In contrast to thermoset resins, thermoplastics addition of a thermoplastic (Bucknall and can be dissolved and melted. In general, vis- Gilbert, 1989) or other means. Although not coelastic and plastic effects are more apparent from the table, epoxy modulus is usupronounced in thermoplastics. A presentation ally slightly higher than for thermoplastics.
Table 6.6 Mechanical properties of thermoplastic resins Material
-__

Tensile modulus E (GPu)

1.l-1.6 2.5-3.8 2.74.0 2.3-3.0 3.2 3.5 3.2 3.1-3.8 2.5 2.6 2.84.4 3.0 3.5 3.7 2.8-3.5

PP PA6,6 PET PC Amorph. PA a-2) PPS (Ryton) PAS (PAS-2) PEEK PSU (Udel P1700) PES (Victrex) PA1 (Torlon) PEI (Ultem) TPI (Avimid K-111) TPI (LaRC-TPI) EP(thermoset)

Tensile strength 0,( M W 3040 50-80 50-70 60-70 100 80 100 90-100 70 80 90-190 105 100 120 40-120

Fract lire toughness G,? (kJ m-2)

-

1.6 0.5-0.9
-

4.0 2.5 1.9

3.4

3.3 1.5 1.8 0.1-0.5

Properties and design considerations 123

Many mechanical properties of composites are dominated by the influence of fiber modulus, fiber strength and fiber volume fraction. This is usually true for longitudinal tensile modulus and strength as well as flexural modulus and strength. For thermoplastic composites based on AS-4 carbon fiber, typical tensile data are: longitudinal tensile modulus E,= 130 GPa, longitudinal tensile strength (5, = 1950 MPa. In the present context, we are more interested in properties dominated by the matrix and the fiber/matrix interface. One such property is the transverse tensile strength of unidirectional laminates. When a multidirectional laminate is loaded in in-plane tension, the first major damage mechanism is likely to be matrix cracking in the plies with transverse orientation to the maximum load direction. This reduces laminate stiffness and initiates other damage mechanisms such as delamination. In Table 6.7, transverse strength and modulus are presented for different thermoplastic composites. Fiber volume fractions are high, V ,= 0.5-0.6, For composites based on brittle epoxies, typical transverse strength is 40 MPa. Composites based on LaRC-TPI, J-2, PAS-2 and K-111 show transverse strengths in the range 3 2 4 1 MPa. Otherwise, typical transverse strengths for thermoplastic composites are in the range 60-90 MPa. Toughened epoxy composites also show fairly high transverse tensile strengths, typically around 75 MPa. The use of transverse tension data in failure criteria will lead to conservative estimates. Data are higher for transverse plies in multidirectional laminates (Berglund, Varna and Yuan, 1991). The modulus data for carbon fiber composites in Table 6.7 appear insensitive to small differences in matrix modulus. Variations in fiber volume fraction and transverse fiber modulus between the materials mask any such effect. The detrimental effect of glass fiber as opposed to carbon fiber is apparent from the GF/PA6,6 and CF/PA6,6 data. GF/PP shows very poor performance, probably due to poor fiber/matrix interfacial adhesion (note the low V, ). Interfacial weakness is also likely to explain the low strength for Kevlar / PEKK. For thermoplastic composites based on AS-4 carbon fiber, Table 6.7 can be used to estimate typical data: transverse

Table 6.7 Transverse tensile properties of thermoplastic composites

Material
GF/PP GF/PA6,6 CF/PA6,6 CF/Am. PA CF/PPS CF/PAS CF/PAS CF/PSU K49/PEKK CF/PEKEKK CF/PEEK CF/PAI CF/TPI CF/TPI CF/TPI CF/EP CF/EP

Transverse modulus Transverse strengfh ET (GPa) (MPa) ~~~

Plytron (V, = 0.35) E-glass/Ultramid G30-500/Ultramid AS-4/J-2 AS-4/Ryton T 650-42/Rade18320 AS-4/PAS-2 AS-4/Udel P1700 Kevlar/PEKK LDFTM G30-500/Ultrapek AS-4/PEEK (ICI) T650-42/PAI-696 AS-4/K-III G30-500/NewTPI AS-4/LaRC-TPI AS-4/3501 (thermoset) HTA/6376C (thermoset)

4 8.6 7.2 9 7.6 8.4 8.3 7 6.2 10.3 8.9 7.6 9 8.3

9 9.9

11 48 72 35 72 61 32 59 21 90 80 67 41 59 33 52 75

124 Thermoplastic resins tensile modulus E, = 8.6 GPa, transverse tensile strength (T, = 75 MPa. High interlaminar toughness is desirable since this suppresses the tendency for delamination crack formation during loading. Interlaminar fracture toughness is determined on double cantilever beam specimens (DCB), usually unidirectional materials are used (Whitney, Browning and Hoogsteden, 1982). In Table 6.8 such data are presented. CF/PEEK shows the highest fracture toughness. All thermoplastic composites show higher toughness than the thermoset composites. There is a difference between crack initiation and crack propagation data (Davies, Benzeggagh and de Charentenay, 1987). The data presented here are crack propagation data; crack initiation data are in general much lower. For tough matrices one may question the applicability of the data to design problems. In DCB experiments, the crack opening displacement (COD) is very high, whereas the COD at small central cracks in stiff laminates is much smaller. Local stress fields and damage mechanisms may therefore be different and affect the measured fracture toughness. At present, delamination fracture toughness from DCB tests are therefore preferentially used to compare material. It has been pointed out that composite data are significantly lower than resin data (Hunston, 1984).In tests
on neat resins, energy is absorbed by yielding and other types of damage when the volume of material is relatively large. In a composite, the presence of fibers tends to limit this material volume. For shear strength, no comparable data for different thermoplastic composites appear to be available in the literature. The interlaminar fracture toughness in mode I1 shear loading, Glrc,is higher for thermoplastic than for comparable thermoset composites (Cantwell and Davies, 1993). This also indicates a higher shear strength for the thermoplastic composites. A typical value for the in-plane shear modulus of thermoplastic composites based on AS-4 carbon fiber is 4.8 GPa which is similar to toughened CF/EP systems but slightly lower than for brittle matrix CF/EP composites. Compressive strength is lower for thermoplastic than for thermoset composites (Table 6.9). Most of the thermoplastic composites are in the range 900-1100MPa whereas typical thermoset composite data are 1700 MPa. Fiber misalignment, shear stiffness and strength have been shown to affect compression strength based on plastic kink band formation (Budiansky, 1983). Compression modulus data in Table 6.9 are similar, in support of similar fiber volume fractions for the materials compared. The composite based on PA6,6 has the lowest strength; PA6,6 also has

Table 6.8 Interlaminar fracture toughness of thermoplastic composites Material

_ _

Trade name
-~ ~

Fracture toughness qc(kJ~m-2) ~

1.3 0.9 2.1 2.5 1.2
1.3 0.9 1.8 0.8 0.2 0.5

CF/Amorph. PA CF/PPS CF/PEEK CF/PEEK CF/PSU CF/PAI CF/PEI CF/TPI CF/TPI CF/EP CF/EP

AS-4/ J-2 AS-4/Ryton AS-4/Victrex PEEK IM7/Victrex PEEK AS-4/Udel P1700 T650/Torlon AIX-159 T300/Ultem 1000 AS-4/Avimid K-I11 AS-4/ LaRC-TPI AS-4/3501-6 (thermoset) IM7/8551-7 (thermoset)

Properties and design considerations

Table 6.9 Compressive properties of unidirectional thermoplastic composites
Material
CFDA6.6 CF/Amorph. PA CF/PPS CF/PAS CF/PEEK CF/PEEK CF /PEKEKK CF/PSU CF/PAI CF/TPI CF/EP CF/EP

125

Trade name
G30-500 /Ultramid AS-4/ J-2 AS-4 / Ryton AS-4/ PAS-2 AS4/Victrex PEEK IM7/Victrex PEEK AS-4/Ultrapek AS-4/Udel P1700 C-3000/Torlon C AS-4/Avimid K-111 AS-4/ 3501-6 (thermoset) HTA/6376C (thermoset)

Compression strength (MPa)

700 1100 940 900 1100 1140 1310 1040 1380 1000 1720 1720

__

-~

Modulus (MPa)
110
-

130 120 120

-

127
-

110 140 130

the lowest creep modulus and yield stress of superior performance to first generation therthe investigated matrices. It is interesting to moset composites (AS-4/3501-6). This is note that AS-4/PEEK and IM-7/PEEK have because the delaminated area due to the roughly the same strength although the IM-7 impact event is more limited for the thermofiber has higher modulus. The smaller diame- plastic composites. However, toughened ter of the IM-7 fiber appears to have a negative epoxy resin composites combined with tougheffect as expected from Euler-buckling consid- ened interlayers between the plies do in erations. general show as good compression strength Compression strength after impact, a mea- after impact as thermoplastic composites. In sure of laminate and material damage fatigue, delamination resistance is higher for tolerance (Dorey, 1989), is presented in AS-4/PEEK compared with epoxy composites Table 6.10. A quasi-isotropic laminate of given (Gustafsson, 1988). However, in uniaxial tenlay-up and geometry is subjected to impact of sion, brittle CF/EP was found to be superior to a certain energy. Internal damage mechanisms both toughened CF/EP and the thermoplastic such as matrix cracking and delamination composite (Curtis, 1987). Claims have been occur in the laminate. The plate is then sub- made that this observation is due to heating jected to compressive load and the stress and effects in the thermoplastic composite specistrain at failure can be determined. The data mens from testing at high frequency (Moore, show that thermoplastic composites have 1991).
Table 6 1 Compression strength after impact of thermoplastic composites .0
Material Trade name Compression strength after impact (impact energy) (28 J) (42 1) (571) o (MPa) o (MPa) o (MPa) 221 179 331 310 290 365 345 317 179 145 131 303 -

CF / PPS CF/PEEK CF / PA1 CF/EP CF/EP

AS-4 /Ryton AS-4/Victrex PEEK C-3000/Torlon C AS-4/3501-6 (thermoset) AS-4/8551-7 (thermoset)

126 Thermoplastic resins

Table 6.11 Glass and heat deflection temperatures for amorphous thermoplastics Table 6.12 Glass melting and heat deflection temperatures for semi-crystalline thermoplastics

Material
PC Amorph. PA PSU PES PA1 PEI EP (thermoset)

T, ("C)
150 160 190 220 290 217 200

HDT ("C)
132 154 175 203 278 200 180

Material
PP PA6.6 PET PPS PEEK TPI (Aurum)

T, ("C) -10 55 70 90 143 250

T,,, ("C)
165 265 265 280 343 388

HDT ("C)
60 75 41 135 160 238

Increased market need for polymer composites with good performance at elevated temperature has generated interest in thermoplastic composites. Materials with continuous use temperatures above 150C are of particular interest since they perform better than epoxies. One question is how maximum use temperature relates to Tg. In Table 6.11, Tg and the heat deflection temperature (HDT) for amorphous thermoplastics are presented. HDT is determined by subjecting the material to static load (typically 1.8 MPa) and slowly increasing the temperature. HDT is determined as the temperature at which a critical deflection of the sample is obtained. Table 6.11 shows HDT to be 620C below the T of amorphous poly6 mers. In comparison with room temperature strength, the strength of the composite is significantly reduced above the HDT. The reason

is that molecular mobility in the polymer is increased dramatically as the temperature approaches T . In Table 8.12, similar data to those in Table 6.11 are presented for semi-crystalline thermoplastics. HDT is usually somewhat higher than Tg. However, for some semicrystalline polymers, HDT is below T (as for amorphous polymers). Creep effects 'will be very strong close to and above Tg.For this reason the maximum temperature for continuous service under significant load is unlikely to exceed a temperature of 20C below T' for semi-crystalline thermoplastics. The primary advantage of crystallinity is therefore chemical resistance. This is apparent from Table 6.13, where chemical resistance for different thermoplastics is indicated in a qualitative way. Semi-crystalline thermoplastics have much

Table 6.13 Chemical resistance of thermoplastics

Material

Structure

Hydraulic fluid

Chlorinated Ketones kydrocarbons

0 0 0 D D 0 D A D 0 0 0 A A 0 A A A

Esters H,O abs. (Yo)

0 0 0 A A
0

PA6,6 PEEK PPS PEI PSU

PA1

PES Am.PA PC

Crystalline Crystalline Crystalline Amorphous Amorphous Amorphous Amorphous Amorphous Amorphous

0 0 0 A 0 A A
-

A A

8 0.5 0.5 1.2 0.9 2 4 0.3 5

-

0 = no effect, A = is absorbed, D = is dissolved

Applications
better chemical resistance than the amorphous polymers. A notable exception is the high water absorption in PA6,6 caused by hydrophilic groups in its chemical structure. The solvent resistance of a large selection of different thermoplastic composites has been reported (Johnston, Towel1 and Hergenrother, 1991). For most thermoplastics, e.g. PEEK, moisture expansion coefficients of the carbon fiber composite may be taken as 0. Thermal expansion coefficientshave been characterized (Barnes et al., 1990) and are similar to epoxy composites. For AS-4/PEEK, the composite density is 1600 kg m-3. For polymers with high Tg, exposure to elevated temperature may lead to increased density not connected with crystallinity but with the amorphous state. The phenomenon is termed physical aging and leads to a more brittle behavior of the polymer (Kemmish and Hay, 1985). Further work is needed to elucidate the importance of physical aging to composite fracture behavior under practical service conditions. For composites processed at high temperatures, residual stresses will also affect fracture behavior. The magnitude of the residual stresses and, consequently, detrimental effects will increase with increasing cooling rate (Manson and Seferis, 1992). Thermoplastic composites can be joined by the same methods as thermoset composites. Bolted joint performance has been compared for thermoset and thermoplastic composites (Walsh, Vedula and Koczak, 1989) with results in favor of thermoplastic composites. With the semi-crystalline thermoplastics, adhesive bonding requires careful surface preparation (Kinloch and Taig, 1987).This is because of the good chemical resistance and limited solubility of these polymers. However, with careful surface preparation, as good adhesive bonds are obtained as with thermoset composites. The thermoplastic nature of the matrix offers another possibility: fusion bonding. Different methods have been compared (Davies and Cantwell, 1993), including hot gas, IR, laser, ultrasonic, vibration, electrical resistance and

127

induction welding. There are difficulties in controlling the processes and very few methods offer the promise of portable equipment. Various bonding technologies for PEEK composites have been compared (Silverman and Criese, 1989).The study favored a technique for fusion bonding with a polyetherimide film. This approach can also be used in repair of damaged structures, since the temperature needed is below the T, of PEEK.
6.6 APPLICATIONS

Thermoplastic composites can be used in similar applications to thermoset composites. The following examples will demonstrate some of the reasons for choosing a thermoplastic composite material. In Europe, the automotive market for GMT composites is significant. Rapid processing by compression molding, cycle times of typically 30s even for large structures, results in cheaper components. In addition, more functions can be integrated into each component compared with sheet metal structures. Bumper beams dominate the automotive market in the US whereas, in Europe, a wider variety of applications are in commercial production. Typical components are subjected to minor loads or impact and surface appearance is not important. Battery trays, beams supporting the hood, seat supports, oil trays, engine shields and even the complete front end have been produced for Volvo, Volkswagen and others. In the aerospace market, DuPont has supplied thermoplastic polyimide composites to the prototype programs for the F-22 fighter aircraft. In the supersonic civil aircraft program, the same thermoplastic polyimide is considered for wing skins. The main reason for this particular thermoplastic composite is a continuous high maximum temperature. AS-4/PEKK (unidirectional discontinuous fibers) was used by Bell Helicopter Textron in a V-22 tiltrotor thermoplastic wing rib for better open hole compression behavior than thermoset composites for high proportions of

128 Thermoplastic resins Bike helmets are also produced (Fig. 6.2). A semi-finished sheet is heated by IR, transfered to heated dies where a selective clamping system is used to hold the sheet. Forming and consolidation pressure is applied and the mold is cooled before demolding. Hoechst in Germany present applications made by winding, a pressure vessel, tubes, sealings and support rings (Fig. 6.3). Matrices include PA6 and PPS with carbon and glass fibers. In the field of biomedical applications, such as hip prostheses, semi-crystalline thermoplastic matrices offer good potential due to their chemical stability (Williams and Fig. 6.2 Bike helmet, an example of a commercial McNamara, 1987).
application of thermoplastic composites (Courtesy: DuPont Europe).

REFERENCES
Astrom, B.T., P.H. Larsson and R.B. Pipes. 1991. Experimental Investigation of a Thermoplastic Pultrusion Process. 36th Int. SAMPE Symp., pp. 1319-30. Barnes, J.A., Sims I.J., Farrow G. et al. 1990. Thermal Expansion Behaviour of Thermoplastic Composite Materials. J Thermoplastic Composites 3: 66-80. Bassett, D.C. 1981. Principles of Polymer Morphology. London: Cambridge University Press. Berglund, L.A. and Ericson M.L. 1994. Glass Mat Reinforced Polypropylene. In Polypropylene: Structure, Blend and Composites. Vol 3: Composites, ed. J, Karger-Kocsis. London: Chapman and Hall. Berglunh L.A., Varna J. and Yuan J. 1991. Effect of Intralaminar Toughness on Transverse Cracking Strain in Cross-Ply Laminates. Adv. Comp. Mater. 1:225-34. Bucknall, C.B. and A.H. Gilbert. 1989. Toughening of a Tetrafunctional Epoxy Resins Using Polyetherimide. Polymer. 30: 213-18. Budiansky, B. 1983. Micromechanics.Computers and Structures. 16 6-10. Cantwell, W.J. and Davies P. 1993. Short-Term Properties of Carbon Fibre PEEK Composites. In Advanced Thermoplastic Composites, ed. Kausch, H-H. pp. 173-191. Munich: Hanser. Carlsson, L.A., ed. 1991. Thermoplastic Composite Materials. Composite Materials Series, Vol 7. New York: Elsevier. Chang, I.Y. 1992. Thermoplastic Matrix Composites Development Update. 37th Int SAMPE Symp.

45" ply angles (probably for decreased tendency to delamination). A female steel tool and matched-die press forming was used (Chang, 1992). A stretch forming process was used to fabricate C-section curved fuselage frames for Boeing Helicopter from AS4/PEKK (Chang, 1992). TenCate in Holland supplies materials for Fokker Special Products. Landing flap ribs and impact resistant ice-protection plates are produced for the Dornier 328 aircraft.

I .:'i
!
1

Fig. 6.3 Thermoplastic composite applications made by winding: pressure vessel, tubes, sealing and support rings. (Courtesy: Hoechst AG)

References 129
Available from DuPont as report entitled Overview of Thermoplastics Composites Technology. Cogswell, EN. 1992. Thermoplastic Aromatic Polymer Composites. Oxford: Butterworth-Heinemann. Cogswell, EN., Hezzell D.J. and Williams P.J. 1981. US Patent 4 549 920. Composites Products Inc 1994. Brochure of CPI process. Winona, Minnesota, USA. Crevecoeur, G. and Groeninckx G. 1992. MeltSpinning of in situ Composites of a Thermotropic Liquid Crystalline Polyester (TLCP) in a Miscible Matrix of Polyether etherketone (PEEK) and Polyether imide (PEI). Polymer Composites 13: 244-50. Curtis, P.T. 1987. In Investigation of the Tensile Fatigue Behaviour of Improved Carbon Fibre Composite Materials. 6th lCCM and 2nd ECCM Proc., Vol 4. pp. 4.544.64. London: Elsevier Applied Science. Davies, P., Benzeggagh M.L. and de Charentenay F.X. 1987. The Delamination Behavior of Carbon Fiber Reinforced PPS. SAMPE Quarterly 19: 19-24. Davies, I? and Canhvell W.J. 1993. Bonding and Repair of Thermoplastic Composites. In Advanced Thermoplastic Composites, ed. Kausch, H-H, pp. 337-366. Munich: Hanser. Dorey, G. 1989. Damage Tolerance and Damage Assessment in Advanced Composites. In Advanced Composites, ed. 1.K Partridge, pp. 369-98. London: Elsevier Applied Science. Egerton, M, and Gruber M. 1988. Thermoplastic Filament Winding Demonstrating Economics and Properties Via In Situ Consolidation. 33rd lnt. S A M P E Symp., pp. 3546. GE Plastics, 1990. Technopolymer Structures, Design and Processing guide. TPS-400A (6/90)RTB. Gustafsson, C-G. 1988. Initiation and Growth of Fatigue Damage in Graphite/Epoxy and Graphite/PEEK Laminates. PhD thesis 88-9. Royal Inst of Techn, Stockholm, Sweden. ISSN 0280-4646. Hartness, J.T. 1982. Polyether-etherketone Matrix Composites. 14th Natl SAMPE Symp., pp. 2643. Hunston, D.L. 1984. Composite Interlaminar Fracture: Effect of Matrix Fracture Energy. Composites Technology Review 6: 176-80. Hoechst AG. 1994. Compela product brochure. Frankfurt am Main, Germany. Howes, J.C., Loos A.C. and Hinkley J.A. The Effect of Processing on Autohesive Strength Development in Thermoplastic Resins and Composites. In Advances in Thermoplastic Composite Materials. ed. G.M. Newaz, ASTM STP 1044, pp. 3349. Philadelphia: American Society for Testing and Materials. Johnston, N.J., Towel1 T.W. and Hergenrother P.M. 1991. Physical and Mechanical Properties of High-Performance Thermoplastic Polymers and their Composites. In Thermoplastic Composite Materials. ed. L.A. Carlsson, Composite Materials Series, Vol 7, pp. 27-71. New York: Elsevier. Kausch, H-H, ed. 1993. Advanced Thermoplastic Composites. Munich: Hanser. Kemmish, D.J. and Hay J.N. 1985. The Effect of Physical Ageing on the Properties of Amorphous PEEK. Polymer 26: 905-12. Kinloch, A.J. and Taig C.M. 1987. The Adhesive Bonding of Thermoplastic Composite. J . Adhesion 21: 291-302. Lee, W.I. and Springer G.S. 1987. A Model of the Manufacturing Process of Thermoplastic Matrix Composites. J. Comp Mater. 21: 1017-55. Manson J-A.E. and Seferis J.C. 1992. Process Simulated Laminate (PSL): A Methodology for Internal Stress Characterization in Advanced Composite Materials. J. Comp Mater. 26: 405-31. Mallon, P.J., O'Bradaigh C.M. and Pipes R.B. 1989. Polymeric Diaphragm Forming of Continuous Fibre Reinforced Thermoplastic Matrix Composites. Composites 20: 48-56. Menges, G. 1966. The reinforcement of plastics. Kunststoffe 56: 818-23. (In German). Moore, D.R. 1991. In Thermoplastic Composite Materials. ed. L.A. Carlsson, Composite Materials Series, Vol 7, pp. 331-69. New York: Elsevier. Olson, S.H. 1990. Manufacturing with Commingeled Yarns, Fabrics and Powder Prepreg Thermoplastic Composite Materials. 35th Int SAMPE Symp., pp. 1306-19. Silverman, E.M. and Criese R.A. 1989. Joining Methods of Graphite/PEEK Thermoplastic Composites. SAMPE Journal 25: 34-38. Sperling, L.H. 1992. Introduction to Physical Polymer Science. New York: John Wiley & Sons. Thiede-Smet, M. 1989. Study of Processing Parameters of PEEK/Graphite Composite Fabricated with 'FIT' Prepreg. 33rd Int SAMPE Symp., pp. 2086-2101. Truckenmueller, F, and Fritz H.G. 1991. Injection Moulding of Long Fibre-Reinforced Thermoplastics: A Comparison of Extruded and Pultruded Materials with Direct Addition of

130 Thermoplastic resins

Roving Strands. Polymer Eng. Sci. 31: 1316-29. Walsh, R, Vedula M. and Koczak M.J. 1989. Comparative Assessment of Bolted Joints in a Graphite Reinforced Thermoset vs Thermoplastic. S A M P E Quarterly 20: 15-19. Whitney, J.M., Browning C.E. and Hoogsteden W. 1982. A Double Cantilever Beam Test for Characterizing Mode I Delamination of Composite Materials. J. Reinforced Plas. and

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Williams, D.F. and McNamara A. 1987. Potential of Polyetheretherketone (PEEK) and CarbonFibre-Reinforced PEEK in Medical Applications. J. Muteu. Sci. Lett. 6 : 188-90.