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CHAPTER 2

Chapter 2 MICRO-BRAIDING FABRICATION METHOD OF CONTINUOUS FIBER REINFORCED CARBON/PEEK COMPOSITE MATERIALS
2.1 Introduction
Composites developed based on thermoplastic matrix materials have several advantages over those based on thermoset materials, such as storage stability without freezing device, higher stability in mechanical performance, cycling usage ability, in-situ adaptability (e.g. through a hot treatment), and so on, and hence have received more attention in recent years. Most such composite products are made by injection

molding which uses pellets of thermoplastic polymers mixed with reinforcing fibers. However, since the reinforcing fibers are generally discontinuous, the usage of the resulting composites cannot be expected at a high stress situation. Hence, in

thermoplastic composite industry, to achieve continuous fiber reinforcement has been a long research topic. The main challenge is a proper impregnation of the

thermoplastic matrix into the reinforcing fibers and uniform fiber dispersion during the processing. viscosity. Unlike thermoset polymers, thermoplastic polymers have relatively high For years, several fabrication methods for continuous fiber reinforced

thermoplastic polymer composites have been developed, as shown in Figure 2.1 [Wakeman et al., 1998]. They are, typically,

1. Film stacking method [Hamada et al., 1998; Gamstedt et al., 1999] (Matrix polymer films and reinforcing fabrics are alternatively interlaced and then hot pressed. This method may be applied to the low viscous polymers with

reinforcing fibers.).

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Reinforcing Fiber Fabric

Polymer Film (a) Film Stacking Method Reinforcing Fiber Yarn Polymer Fiber Yarn

Reinforcing Fiber Yarn

(b) Plied Matrix Method

Polymer Powder (c) Powder Method


Figure 2.1 Schematic drawing of conventional fabrication methods of continuous fiber reinforced thermoplastic composite materials; (a) Film stacking method, (b) Plied matrix method and (c) Powder method. Original drawings of (b) and (c) are referred from Wakeman et al., 1998.

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Reinforcing Fiber Yarn

Polymer Fiber Yarn (d) Co-Woven Method

Reinforcing Fiber

Polymer Fiber

(e) Commingled Yarn Method


Figure 2.1 (continued) Schematic drawing of conventional fabrication methods of continuous fiber reinforced thermoplastic composite materials; (d) Co-woven method and (e) Commingled yarn method. Original drawings of (d) and (e) are referred from Wakeman et al., 1998.

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2. Plied matrix method [Lynch 1989] (Polymer fiber yarn is wound around a reinforcing fiber yarn.).

3. Powder method [Wittich and Friedrich, 1988; Karger-Kocsis et al., 1996 (a); Sala and Cutolo, 1996; Miller et al., 1996; Rath et al., 1998; Wakeman et al., 1998; Chen et al., 1999] (Polymer powder is combined with reinforcing fibers. In addition, matrix film can be used to encapsulate the outside fiber yarn. One

problem with this method is in handling the constituent materials since the polymer powder can easily be dislodged from the reinforcing filaments.).

4. Co-woven method [Clemans et al.,1987] (Matrix fiber yarn and reinforcing fiber yarn are combined as woven form which possesses good drapeability. The

warp direction of a fabric contains all the reinforcing fiber yarns and the weft direction contains all the matrix fiber yarns.).

5. Commingled yarn method [Fujita et al., 1993; Ye et al., 1995; Diao et al., 1997; Lauke et al., 1998; Miller et al., 1998; Karger-Kocsis and Czigany,1998; Long et al., 2001] (Reinforcing and polymer fibers evenly mixed as one yarn. Since

polymer fibers and reinforcing fibers are intimately mixed, good impregnation of the matrix in the fibers and a homogeneous distribution of reinforcement can be expected during the processing).

These methods have been applied to fabricate unidirectional laminated composites and allow good matrix impregnation into reinforcing fabrics. Amongst them, the

commingled yarn and co-woven methods have been mainly used to fabricate textile fabric reinforced composites because of their good drape ability to form the textile fabrics. However, the current co-woven and commingled yarn methods are not 32

CHAPTER 2 flexible enough to fabricate some types of textile fabric reinforced composites. For

example, in order to obtain different mechanical properties of the textile fabric composites, various numbers of material systems (such as glass / nylon, carbon / PET etc.), various sizes of fiber yarns and various mixing ratios of matrix and reinforcing fibers must be applicable. In fact, there are not so many companies in the world Hence, it is not easy to design

which provide products satisfying all of these needs.

the textile composite bone plates based on the application. It should be noted that, in terms of material system of carbon fiber and poly-ether-ether-ketone (PEEK) which will be used for composite compression bone plate development in this thesis, only two companies are available [BASF and Hoechest (both in Germany)] supply commingled yarns [BASF: Ye et al., 1995; Beehag and Ye, 1996; Diao et al., 1997; Karger-Kocsis et al., 1997, Hoechest: Karger-Kocsis et al., 1996 (b)]. Based on such market

situation, Prof.H.Hamada at Kyoto Institute of Technology, one of the supervisors of the current author, previously developed a micro-braiding fabrication method to supply flexible material design on continuous fiber reinforced thermoplastics composites [Sakaguchi et al., 2000]. commingled yarns. The developed method allows many design choices of

Furthermore, high matrix impregnation and good fiber dispersion

can be expected since the reinforcing fibers and the matrix fibers can be combined as one braided yarn. However, since Prof.H.Hamada and his colleague utilized

polyamide as matrix which has greatly low viscosity as compared to PEEK (PA: = 175 Pas, PEEK: = 380 Pas [Astrom, 1997]), there was a need to investigate whether micro-braiding fabrication would be applicable to the composites with high viscous thermoplastics polymers.

Hence, in this chapter, the micro-braiding fabrication method has been further improved to meet with high viscous PEEK. The newly developed micro-braiding

method in this chapter has been expected high matrix impregnation and good fiber dispersion using high viscous thermoplastics polymers. It is well known that the 33

CHAPTER 2 mechanical properties of thermoplastic composites are affected by fabrication conditions, such as pressure, temperature, holding time and cooling history. In other

words, different fabrication conditions will influence the impregnation of molten polymer into reinforcing fibers, the dispersion manner of the fibers and the degradation behavior of the polymer. In terms of the carbon/PEEK material system, several

literature reports are available which discussed the optimum fabrication conditions to get their best mechanical properties [Lustiger et al., 1990; Colel and Casella, 1993; Jar and Kausch, 1994; Lystrup and Anderson, 1998]. However, almost all of the reports It

targeted unidirectional composites made of prepreg sheet supplied by ICI, UK.

must be noted that prepreg sheets already contain impregnated PEEK into carbon fiber fabric. Hence, it is considered that the successful fabrication methods shown in the past reports cannot be applied to the fabrication condition used in this chapter.

The primary objective of this chapter is to discuss the optimum fabrication condition of carbon/PEEK composites fabricated by the newly developed micro-braiding fabrication method. Unidirectional carbon fiber reinforcement with a rectangular specimen shape The

has been adopted to investigate the basic bending property of composite plates.

composite plates have been fabricated at three different fabrication temperatures and three holding times (i.e., nine different fabrication conditions) and their bending properties have been discussed from thermal and fracture characterization. Finally,

the optimum fabrication condition to make textile composite bone plates has been decided by comparing thus obtained results in this chapter.

2.2 Micro-Braiding Fabrication Method


The micro-braiding fabrication method uses conventional braiding technique which is familiar in textile industry. In Japan, the braided fabrics have been originally used as Around 17th to 19th centuries, many braiding craftsmen

accessories from 4th century.

gathered at Edo (present Tokyo) to supply decoration of samurai equipment, such as 34

CHAPTER 2 Japanese swords and armors (see in Figure 2.2) [Tada, 1998]. The yarns made by

the micro-braiding method, so called micro-braided yarns have the feature that the reinforcing and matrix fibers are easily mixed using a simple braiding technique. The

desired size of the micro-braiding yarn can be flexibly designed by choosing suitable sizes of the reinforcing and matrix fiber yarns.

Figure 2.2 Braiding craftsman in Edo Period in Japan [Original figure is referred from Tada 1998]. Conventional braided fabrics are mainly classified into two types; namely, tubular and flat braided fabrics, as shown in Figure 2.3. The surface of the braided fabric shows

a zigzag pattern since fiber bundles alternatively pass over and under continuously. Additional fiber yarns can be inserted into a braided fabric as middle-end-fibers or axial fibers (see Figure 2.3 (a)). The preform condition of a braided fabric is determined by

the combination of the spindle movement and taking up movement of the braiding machine, as shown in Figure 2.4. wound. Spindle is holding a bobbin in which fiber yarn is

Spindle moves along the orbit of the braiding machine and all yarns are

gathered at the preform point, where braided fabric is formed with certain braiding angle. The preformed braided fabric has an intersection repeat pattern, either a

diamond braiding structure or a regular braiding structure, as illustrated in Figure 2.5. 35

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Axial Fiber Yarn

(a)

(b)

Middle-End-Fibres

Braided Yarns

Figure 2.3 Schematic drawing of (a) tubular braided fabrics (Middle-End-Fibres and axial fibre yarn can be inserted) and (b) flat braided fabrics.

(a)

(b)

Braid Fabric

Fiber Yarn Spindle

Taking Up Preform Point

Figure 2.4 (a) Photograph and (b) schematic drawing of a braiding machine.

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(a)

(b)

Diamond Braiding (1/1 intersection)

Regular Braiding (2/2 intersection)

Figure 2.5 Structure of braiding fabrics: (a) Diamond braiding, (b) Regular braiding.

The diamond braiding fabric has a 1/1 intersection repeat pattern, in which a fiber yarn continuously passes over and under one fiber yarn with a braiding angle. The regular braided fabric has a 2/2 intersection repeat pattern, in which a fiber yarn passes over and under two fiber yarns with a braiding angle. The choice of the intersection repeat When all the number of

pattern is determined by the number of used spindles.

spindles is used, the braided fabrics have regular braiding structure. On the other hand, the diamond braiding structure can be made when the half number of spindles is used.

As seen in Figure 2.6 (a), several types of micro-braided yarns can be resulted by varying combination manner between the matrix and the reinforcement fibers [Sakaguchi et al., 2000]. In order to get good matrix impregnation and fiber

dispersion, it is suggested that tow size of reinforcement fiber yarns should be as small as possible and the fiber yarns be placed as several middle-end-fibers [Sakaguchi et al., 2000] (see Type M5). The micro-braided yarn used in this thesis was preformed 37

CHAPTER 2

(a)
MiddleMiddle-EndEnd-Fiber Axial Fiber

Type M5

Type M

Type S

Type A

(b)
Carbon Yarn (black color)

PEEK Yarn (white color)

Figure 2.6 (a) Schematic drawing of several micro-braided yarns [Original drawing is referred from Sakaguchi et al., [Sakaguchi et al., 2000]. Type A: Reinforcement fiber yarn was inserted as axial fiber. Type M5, M and S: Reinforcement fiber yarns were inserted as middle-end-fiber. Type M5 has the smallest tow size of yarn.] and (b) preformed micro braided yarn: 3 carbon fiber yarns were inserted as middle-end-fibers and 10 PEEK yarns were used as braided yarns. using a tubular braiding machine whose spindle number is 20. The micro braiding

yarn shown in Figure 2.6 (b) was preformed, in which three carbon fiber yarns (diameter = 7m, 1000 filaments: Toray Co., Ltd., Japan), all as middle-end-fibers, were inserted in a tubular braided fabric of 10 PEEK fiber yarns (yarn size = 230dTEX, 30 filaments: ZYEX Co., Ltd., UK). The preformed yarn has a diamond braiding 38

CHAPTER 2 structure. As seen in Figure 2.7, PEEK has three benzene rings in a unit of chemical structure which leads to the rigid movement of the chain. Hence, PEEK has relatively

high glass transition temperature (Tg) and melting temperature (Tm) as compared to other engineering polymers such as polyolefin and polyamide. According to the

company datasheet, Tg and Tm of the used PEEK fiber yarns are 143Co and 334 Co, respectively. More detailed information about PEEK polymer can be found in some

material handbooks [Beland, 1990; Fried, 1999].

[O

O O C

]n

Figure 2.7 Chemical structure of poly-ether-ether-ketone (PEEK).

Unidirectional laminated carbon/PEEK composite plates were fabricated following the below sequence: (see Figure 2.8).

(a)

(b)

Figure 2.8 Compression molding of unidirectional carbon/PEEK composites. (a) Micro braiding yarn was wound around a stainless-steel frame and a frame was placed into (b) a stainless-steel molding.

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CHAPTER 2 1. Micro-braided yarn was unidirectionally wound around a stainless-steel frame with a proper tension.

2. Silicon gel (Shinetsu-Chemical Co., Ltd., Japan) was spread on the surface of a stainless-steel molding for the releasing purpose of the material. The frame was then placed in the molding.

3. The molding was placed on the table of a hot press machine (see Figure 2.9).

4. The press machine was operated by a computer program which decides a history of temperature, pressure, holding time and cooling rate, as shown in Figure 2.10. In this chapter, three different temperatures (i.e., 380oC,

410oC and 440oC) and three holding times (i.e., 20, 40 and 60 minutes) were adopted to investigate the quality (matrix impregnation and void existence) of the resulting unidirectional carbon/PEEK composite plates. The applied pressure was fixed at 4.4MPa and this pressure value was relatively high as compared to the other unidirectional carbon/PEEK composites made of the commingled yarn (0.5 ~ 3MPa [Ye et al., 1995], 0 ~ 1MPa [Beehag and Ye, 1996]. It was considered that fabrication

temperature and holding time were more dominant under 4.4MPa pressure. Hence, nine different types of composite plates were fabricated. The

temperature increased up from room temperature (25oC) to the fabrication temperature in about 9oC/min heating speed without pressure. After that, When

the pressure was eventually applied to the molding for 10 minutes.

the pressure reached the setting value (4.4MPa), the temperature and the pressure were maintained for 20 minutes. Finally, gradual cooling

(average cooling rate = -5oC/min) was applied to the molding till room 40

CHAPTER 2 temperature.

5. The fabricated composite plates were removed from the stainless-steel molding and were cut with specimen length, as shown in Figure 2.11.

Figure 2.9 Photograph of the hot press machine.

Temp.

Fabrication Temp.: 380oC, 410oC and 440oC

Cooling Rate: - 5OC / min

Pressure (4.4MPa) 25oC


10min

Time
Holding Time: 20min, 40min, and 60min

Figure 2.10 Fabrication conditions of unidirectional carbon/PEEK composite plates.

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1cm

Figure 2.11 Photograph of fabricated unidirectional carbon/PEEK composite plates.

Fiber volume fraction of the fabricated composites was calculated by a burning method. Each cut sample was put in a small ceramic pot. reached 550oC, it was hold for 1.5hours. When temperature of the furnace

After the PEEK polymer was completely

burnt, the weight of the remaining carbon fibers was measured and the weight of the PEEK was automatically calculated from the original sample weight. Using densities

of 1.3g/cm3 for the PEEK and 1.7g/cm3 for the carbon fibers, the fiber volume fraction was calculated for each sample. composite plates was 41.6%. The averaged fiber volume fraction of the fabricated

2.3 Experimental Procedure


In order to investigate the thermal behavior of the PEEK matrix under nine fabrication conditions, neat PEEK fiber yarns were subjected to three heating treatments and their thermal behavior was characterized by TGA (Thermo gravimetric Analysis). Bending

property of the composite plates was characterized through four-point bending tests and fracture analysis.

2.3.1 Thermo Gravimetric Analysis (TGA) Characterization


Neat PEEK fiber yarns were subjected to three heating histories of (a) Non-treatment, (b) 380oC for 20 minutes and (c) 440oC for 60 minutes. The condition (b) corresponds

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CHAPTER 2 to the lowest fabrication temperature and the shortest fabrication time while the condition (c) corresponds to the highest fabrication temperature and the longest fabrication time. With these conditions, thermal behavior of the PEEK fibers was

characterized by TGA (TA Instruments Pte., Ltd) in a temperature range from 30oC to 700oC with a heating rate of 20oC/min. Each sample amount was 10mg.

2.3.2 Four-point Bending Test


Four-point bending tests were performed on an Instron universal testing machine (Model: 4303) for the fabricated unidirectional carbon/PEEK composite plates with a cross-head speed of 3.0mm/min. and 50%, respectively. The testing temperature and humidity were 25oC

For each type of specimen, a minimum number of four

specimens have been tested until their ultimate fracture. Figure 2.12 shows that the beam specimens had a support span (the distance between the two supporting points) of 73mm, width of 15mm, and a load span of 41mm (the distance between the two loading points). The root radius of the 4 supports was 5mm. From the

load-deflection curve, the bending modulus E and bending strength are derived from the classical beam theory as follows:

1) E = m (a2/3h)(3b/a + 2),

2) = 3Pmax a / (bh2),

where m is the slope of bending stress-deflection curve in a range of displacement from 1mm to 2mm, a is the length (=16mm) of [(support span load span)/2], b is the beam width (=15mm), h is the beam thickness, and Pmax is the maximum applied load.

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41 15 2.809 + 0.067

73 93 Unit: mm

Figure 2.12 Schematic drawing of a bending specimen of unidirectional carbon/PEEK composite plates. Upper and lower span lengths are 41mm and 73mm, respectively.

2.4 Results 2.4.1 TGA Analysis


As shown in Figure 2.13, weight residue of the PEEK fibers subjected to each treatment remarkably dropped in a temperature range between 550oC and 580oC. In

the case of (a) non-treatment and (b) 380oC20 min treatment, the temperature which showed a 5% residual weight decrease was 561oC. In the contrast, the PEEK fibers of (c) 440oC60 min treatment showed a 5% residue decrease at 553oC.
Non-treatment 380oC 20min 440oC 60min

Weight Residue (%)

110 100 90 80 400 450 500


553oC 561oC

550

600

Temperature (oC) Temp (degree)

Figure 2.13 TGA curves of PEEK fibers experienced (a) Non-treatment, (b) 380oC-20min and (c) 440oC-60min heat treatments. 44

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2.4.2 Bending Performance


Figure 2.14 shows the bending stress - displacement curves of the composite specimens fabricated at 380oC, 410oC and 440oC respectively. In the case of

specimens fabricated at 380oC and 410oC, the bending stress linearly increased with the increase of displacement no matter which holding time was applied. After the

stress reached the maximum value, specimen fracture was observed and the bending stress simultaneously dropped to zero. With respect to the specimens fabricated at However, the The

440oC, all curves also showed a linear bending stress increase.

specimen of the 60 minutes holding time fractured at a lower stress value.

relationship between the bending modulus and the holding time is summarized in Figure 2.15. The bending modulus was not changed with increasing the holding time The bending modulus was around

for the specimens fabricated at 380oC and 410oC. 95GPa.

It is noted that a slight modulus drop was seen in the case of 440oC The similar tendency was also seen in the bending strength, as shown in The bending strength showed around 1300MPa, in the case of 380oC In the contrast, the 440oC specimens indicated

specimen.

Figure 2.16.

and 410oC fabrication temperatures.

that the bending strength dropped about 200MPa from the 40 minutes to the 60 minutes holding time.

2.4.3 Fracture Observation


As seen in Figure 2.17 (a), the composite plates fabricated at 380oC for the 20 minutes holding time showed delamination at the tensile side. further examined (see Figure 2.17 (b)). The delamination part was

It was seen that the geometry of fiber yarns

was unchanged inside the specimens and a large crack propagation was recognized between the fiber yarns wherein. Figure 2.18 shows the fracture photo of the Except for a large main

specimen fabricated at 380oC for 60 minutes holding time.

crack, several numbers of sub cracks were observed which mean that the increase in

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1400 Bending Stress (MPa) 1200 1000 800 600 400 200 0 0 1 2 3 4 5 6 Displacement (mm) 1400 Bending Stress (MPa) 1200 1000 800 600 400 200 0 0 1 2 3 4 5 6 Displacement (mm) 20min 40min 60min 20min 40min 60min

380oC

410oC

1400 Bending Stress (MPa) 1200 1000 800 600 400 200 0 0 1 20min 40min 60min

440oC

Displacement (mm)
Figure 2.14 Bending stress displacement curves of unidirectional carbon/PEEK composite plates fabricated at 380oC, 410oC and 440oC.

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Bending Modulus (GPa)

110 100 90 80 70 60 50 0

380oC
20 40 60 80

Holding Time (minutes)

110 Bending Modulus (GPa) 100 90 80 70 60 50 0

410oC
20 40 60 80

Holding Time (minutes)


Bending Modulus (GPa) 110 100 90 80 70 60 50 0

440oC
20 40 60 80

HoldingTime Time(minutes) (minutes) Holdinh

Figure 2.15 Relationship between bending modulus and holding time under the pressure on carbon/PEEK composite plates fabricated at 380oC, 410oC and 440oC.

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Bending Strength (MPa)

1400 1300 1200 1100 1000 900 0

380oC
20 40 60 80

Holding time (minutes)


Bending Strength (MPa) 1400 1300 1200 1100 1000 900 0

410oC
20 40 60 Holding time (minutes) 80

1400 Bending Strength (MPa) 1300 1200 1100 1000 900 0

440oC
20 40 60 80

Holding time (minutes)

Figure 2.16 Relationship between bending strength and holding time under the pressure on carbon/PEEK composite plates fabricated at 380oC, 410oC and 440oC. 48

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Figure 2.17 Fracture aspect of unidirectional carbon/PEEK composites fabricated at 380oC for 20 minutes; (a) whole fracture aspect and (b) cross-section A-B.

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Figure 2.18 Fracture aspect of unidirectional carbon/PEEK composites fabricated at 380oC for 60 minutes.

Figure 2.19 Cross-section of unidirectional carbon/PEEK composites fabricated at 440oC for 60 minutes.

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CHAPTER 2 the fabrication time gave some influence on the crack propagation. In the case of the

highest fabrication temperature 440oC, a similar fracture manner was observed with all the holding times. However, as indicated in Figure 2.19, some large voids and micro

voids was observed in the cross-section of the composite specimens with the 60 minutes holding time.

Figure 2.20 shows delaminated layers of the specimens fabricated at 380oC for 20 minutes and 440oC for 60 minutes. It was found that the delaminated part has a rust

color in the case of the specimen fabricated at 440oC for 60 minutes whereas the other specimen remains the original cream color of the PEEK material. Furthermore, those

delaminated layers were observed under scanning electron microscope, as shown in Figure 2.21. It was shown that (a) ductile fracture manner of the PEEK matrix and (b)

a number of river marks were observed in the specimen fabricated at 380oC for 20 minutes. On the other hand, exposed carbon fibers were remarkably observed in the These results suggest that crack

specimen fabricated at 440oC for 60 minutes.

propagated into the resin region in the case of 380oC-20min specimen while crack propagation occurred at interphase between fiber and matrix for 440oC-60min specimen.

(a) 380oC 20min

(b) 440oC 60min

Figure 2.20 Photograph of delaminated layer of unidirectional carbon/PEEK composite plates fabricated at (a) 380oC 20min and (b) 440oC 60min. 51

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380oC 20min
(a) (b)

river mark Ductile PEEK Fracture

440oC 60min
(c) Exposed Fibers (d)

Figure 2.21 SEM fracture aspect of delaminated layer of carbon / PEEK composite plates fabricated at 380oC for 20 minutes and 440oC for 60 minutes.

2.5 Discussion
In the literature, several researches have been undertaken to investigate the influence of fabrication conditions on the mechanical property of carbon/PEEK composite materials [Lustiger et al., 1990; Colel and Casella, 1993; Jar and Kausch, 1994; Lystrup and Anderson, 1998]. However, it must be realized that almost all of the

previous efforts have been focused on unidirectional composites made of the prepreg sheets supplied by ICI, UK. Since these prepreg sheets contain impregnated PEEK

matrix within the carbon fibers, the polymer impregnation morphology is obviously different compared to the composites made of commingled yarns. In other words, the

fabrication conditions obtained in the past cannot be applied to the composites made 52

CHAPTER 2 of the present minor-braided yarns.

Hence, in this chapter, unidirectional carbon/PEEK composites were fabricated at 380oC, 410oC and 440oC with varying holding times, i.e., 20, 40 and 60 minutes respectively. As shown in Figures 2.15 and 2.16, bending stiffness and bending

strength of the composites decreased with the increase of holding time at the 440oC fabrication temperature. According to the tolerance exposure time of bulk PEEK in

presence of oxygen at elevated temperatures [Astrom 1997], about 30 minutes is the limit to expose PEEK at 380oC. This tolerance time eventually decreases with Hence, it was highly possible that the PEEK

increasing the exposed temperature.

matrix property might have degraded during the fabrication process and the degradation could be remarkable with the higher fabrication temperature and the longer holding time. As seen from the TGA data (Figure 2.13), the PEEK fibers with

440oC-60min heat treatment indicated the 5% weight residue drop at a lower temperature compared with the PEEK fibers with other treatments. The TGA results

showed the fact that the PEEK matrix property in a composite degraded by increasing the fabrication temperature and the holding time. This degradation phenomenon

supports that pretty amount of macro and micro voids existed in the specimen fabricated at 440oC for 60 minutes (see Figure 2.19). Moreover, in this specimen, it

must be noticed that the crack propagation might occur at interphase between fibers and matrix (see Figure 2.21), which would have attributed to the scatter of the bending strength tested from the 440oC-60min specimens.

Bending performances of both the specimens (380oC -20min and 380oC-60min) are the same under a static loading. However, as seen in Figure 2.17, the 380oC - 20min

specimen only had a large main crack whereas several sub-cracks were generated when the holding time increased to 60 minutes (see Figure 2.18). change of this fracture aspect is due to the degradation of PEEK. It is likely that the Hence, when the 53

CHAPTER 2 specimen is subjected to a fatigue load, crack propagation might occur from the degraded PEEK matrix. In such case, there is a possibility that the 380oC 60min

specimen may show a lower bending property than the 380oC 20min specimen. In this case, longer disposure time of the material is not preferable.

The above results suggest that a lower fabrication temperature and a shorter holding time are required to obtain carbon/PEEK composites based on a commingled yarn technique. It must be noted that even under the condition of 380oC fabrication

temperature and 20 minutes holding time the matrix degradation might have occurred at the surface of the specimens. However, below this temperature resulted in a poor Hence, the 380oC fabrication

impregnation since the viscosity of PEEK is still high.

temperature and the 20 minutes holding time are recommended for the fabrication of carbon/PEEK composites using the micro-braiding processing method.

2.6 Conclusions
In this chapter, a micro-braiding fabrication method was developed which will be used in subsequent chapters for the fabrication of textile carbon/PEEK composite compression bone plates. In order to investigate an optimum fabrication condition,

unidirectional carbon/PEEK composite plates were obtained under 9 different fabrication conditions. Bending performance of the fabricated composites was The bending performance was not However,

significantly affected at 440oC temperature.

changed at the 380oC and 410oC temperatures with all the holding times.

the TGA result and fracture observation suggested that degradation of PEEK matrix might initially occur at the surface and eventually at the inside part of the specimen. Hence, the 380oC temperature and 20 minutes holding time are recommended for unidirectional carbon//PEEK composite plate fabrication in order to minimize the PEEK degradation. Under this condition, the composite plates exhibited an excellent

bending performance (i.e., 95GPa bending modulus and 1300MPa bending strength). 54

CHAPTER 2 It can be considered that the micro-braiding fabrication method is an excellent fabrication method for continuous fiber reinforced carbon/PEEK composite materials. In the next two chapters, the optimum fabrication condition obtained in this chapter will be applied to fabricate textile carbon/PEEK composite compression bone plates. Accordingly, their bending performance will be investigated.

References
1) Astrom, B.T., Manufacturing of Polymer Composites, Champman & Hall, pp.65, pp.140, 1997. 2) Beehag, A., and Ye, L., Role of Cooling Pressure on Interlaminar Fracture Properties of Commingled Carbon/PEEK Composites, Comp Part A, 27A, 175-182, 1996. 3) Beland, S., High Performance Thermoplastic Resins and their Composites, Noyes Data Corporation, 33-35, 1990. 4) Chen, J.H., Schulz, E., Bohse, J., and Hinrichsen, G., Effect of Fibre Content on the Interlaminar Fracture Toughness of Unidirectional Glass-Fibre/Polyamide Composite, Comp Part A, 30, 745-755, 1999. 5) Clemans, S., Western, E., and Handermann, A., Hybrid Yarns for High-Performance Thermoplastic Composites, Looking Ahead for Materials and Processes, Vol.1, eds.J.d. Bossu and P.Lissac. Elsevier Science Publishers B.V., Amsterdam, 1987. 6) ColeI, K.C., and Casella, G., Fourier Transform Infra-Red Spectroscopic Study of Thermal Degradation in Poly(ether ether ketone)-Carbon Composites, Polymer, 34, 4, 740-745, 1993. 7) Diao, X., Ye, L., and Mai, Y.-W., Fatigue Behaviour of CF/PEEK Composite Laminates made from Commingled Prepreg. Part I: Experimental Studies, Comp Part A, 28A, 739-747, 1997. 8) Fujita, A., Maekawa, Z., Hamada, H., Matsuda, M., Matsuo, T., Mechanical Behavior and Fracture Mechanism of Thermoplastic Composites with Commingled Yarn, J Reinf Plast Comp, 12, 156-172, 1993. 9) Fried, J.R., Poly(ether ether ketone), Polymer Data Handbook, Oxford University Press, pp.466-470, 1999. 10) Gamstedt, E., Berglund, L., and Peijs, T., Fatigue Mechanisms in Unidirectional Glass-Fiber-Reinforced Polypropylene, Comp Sci Tech, 59, 759-768, 1999. 11) Hamada, H., Fujihara, K., and Harada, H., "Influence of Sizing Agents on Bending Property of Continuous Glass Fiber Reinforced Polypropylene Composites", Comp, 55

CHAPTER 2 31, 9, 979-990, 2000. 12) Jar, P. -Y. B., and Kausch, H. -H., The Influence of Moulding Conditions on Delamination Behaviour of Carbon-fibre/peak Composites, Comp Sci Tech, 52, 3, 349-359, 1994. 13) Karger-Kocsis, J., Czigany, T., and Mayer, J., Fracture Behaviour and Damage Growth in Knitted Carbon Fibre Fabric Reinforced Polyethylmethacrylate, Plast Rub Comp Proces Appl, 25, 3, 109-112, 1996 (a). 14) Karger-Kocsis, J., Czigany, T., Gaal, J., and Ostgathe, M., Stiffness and Strength Anisotropy in the Tensile Response of Weft Knitted Fabric-Reinforced PEEK- and PET-Composites, Adv Comp Lett, 5, 3, 71-75, 1996 (b). 15) Karger-Kocsis, J., and Yuan, Q., Mayer, E., and Wintermantel, E., Transverse Impact Behavior of Knitted Carbon-Fiber Fabric-Reinforced Thermoplastic Composites Sheets, J Therm Comp Mater, 10, 163-172, 1997. 16) Karger-Kocsis, J., and Czigany, T., Effects of Interphase on the Fracture and Failure Behaivior of Knitted Fabric Reinforced Composites produced from Commingled GF/PP Yarn, Comp Part A, 29A, 1319-1330, 1998. 17) Lauke, B., Bunzel, U., and Schneider, K., Effect of Hybrid Yarn Stucture on the Delamination Behavior of Thermoplastic Composites, Comp Part A, 29A, 1397-1409, 1998. 18) Long, A.C., Wilks, C.E., and Rudd, C.D., Experimental Characterization of the Consolidation of a Commingled Glass/Polypropylene Composite, Comp Sci Tech, 61, 1591-1603, 2001. 19) Lustiger, A., Uralil, F.S., and Newaz, G.M., Processing and Structural Optimization of PEEK Composites, Polym Comp, 11, 1, 65-75, 1990. 20) Lynch, T., Thermoplastic / Graphite Fiber Hybrid Fabrics, SAMPE Journal, 25, 1, 17-22, 1989. 21) Lystrup, A., and Andersen, T.L., Autoclave Consolidation of Fibre Composites with a High Temperature Thermoplastic Matrix, J Mater Proces Tech, 77, 1-3, 80-85, 1998. 22) Miller, A., Wei, C., and Gibson, A.G., Manufacture of Polyphenylene Sulfide (PPS) Matrix Composites via the Powder Impregnation Route, Comp Part A, 27A, 49-56, 1996. 23) Miller, A.H., Dodds, N., Hale, J.M., and Gibson, A.G., High Speed Pultrusion of Thermoplastic Matrix Composites, Comp Part A, 29A, 773-782, 1998. 24) Rath, M., Kreuzberger, S., and Hinrichsen, G., Manufacture of Aramid Fibre Reinforced Nylon-12 by Dry Powder Impregnation Process, Comp Part A, 29A, 933-988, 1998. 25) Sakaguchi, M., Nakai, A., Hamada, H., and Takeda, N., The Mechanical Properties of Unidirectional Thermoplastic Composites Manufactured by a Micro-braiding technique, Comp Sci Tech, 60, 717-722, 2000. 56

CHAPTER 2 26) Sala, G., and Cutolo, D., Heated Chamber Winding of Thermoplastic Powder Impregnated Composites: Part 1. Technology and Basic Thermoplastic Aspects, Comp Part A, 27A, 387-392, 1996. 27) Tada, M., "Japanese and Andean Braids", Proc the 4th Int Symp Tex Comp, O-41-1 ~ O-41-8, 1998. 28) Wakeman, M.D., Cain, T.A., Rudd, C.D., Brooks, R., and Long, A.C., Compression Moulding of Glass and Polypropylene Composites for Optimized Macro- and MicroMechanical Properties 1 Commingled Glass and Polypropylene, Comp Sci Tech, 58, 1879-1898, 1998. 29) Wittich, H., and Friedrich, K., Interlamina Fracture Energy of Laminates made of Thermoplastic Implegnated Fiber Bundles, J Therm Comp Mater, 1, 221-231, 1988. 30) Ye, L., Friedrich, K., Kastel, J., and Mai, Y.-W., Consolidation of Unidirectional CF/PEEK Composites from Commingled Yarn Prepreg, Comp Sci Tech, 54, 349-358, 1995.

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