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Synthesis and Characterization of Alumina nanofiber Reinforced Poly ether ether ketone (PEEK) Tg. Mahizatulazwa Tg.

Kamaruddin, Mohamad Ridzuan Nordin, Izan Izwan Misnon, Yusof Hashim Faculty of Science Industry and Technology, University Malaysia Pahang


The papers concerns on the dispersion of the fillers in the polymer matrix. Alumina nanofiber was chosen as a filler to incorporate with PEEK. Improvement of Poly ether ether ketone (PEEK) properties can be achieved by well dispersed of alumina nanofiber within PEEK matrix. In this study,an ultrasonic bath was used in dispersing the alumina nanofiber . TGA/DTG curves have proved that alumina nanofiber has caused greater stability to PEEK. Transmission electron microscopy (TEM) have confirmed that alumina nanofiber have been well dispersed and distribute in PEEK matrix. The optimum sonication time were observed at 30 minutes.



The field of composite materials has had the attention of scientist and researchers. Fiber reinforced composites consist of fibers of high aspect ratio as the dispersed phase. The interest part, when the nanofiber are mixed with polymer matrix, the nanocomposites have been applied in the commercial and industrial field [1]. They are used widely especially in aircraft, space, automotive, sport, plastic and electronic industries. In recent years, high performance engineering plastics has become commercially available, high performance poly (ether ether ketone) (PEEK) polymer was successfully prepared by Bonner in 1962 [3]. PEEK is a semicrystalline thermoplastic with outstanding performances. It possess posses excellent mechanical properties like strength, modulus, toughness, resistance to creep, abrasion and fatigue), high temperature resistant, high continous service temperature, good resistance to aggressive solvent, and being completely soluble in concentrated sulphuric acid at room temperature [11-13]. These features have become an attractive matrix material in producing nanocomposites for engineering purpose. There are a lot of study have been done in incorporating PEEK with nanofillers. Kuo et al. [2] reinforced PEEK with alumina nanoparticles and investigated the effect of filler content on the properties of the resulting nanocomposites. They reported improvements in the tensile modulus and strength; however there was reduction in the failure strain with addition of nanoparticles. They observed that the optimum particle content to achieve the best improvement

in properties is about 5-7%. Goyal et al. [3] reported that adding alumina nanoparticles to PEEK improves the storage modulus and wear resistance of PEEK. The composites in their study were prepared by compression molding. Guoliang et al. [4] used four different methods to disperse nanoparticles in PEEK. Their results also shows that the thermal properties of the composites increased by adding the nanoparticles.The primary objective of this study is to process PEEK composites with well dispersed and homogenous distribution nanofillers and evaluate the mechanical and thermal behavior of reinforcement of nanofillers with PEEK.The details of processing, test methods used and the results obtained are discussed in the subsequent sections of the paper.

2. 2.1

Experimental Materials

Materials used for synthesizing of alumina nanofiber consists Aluminium Ispopropoxide (Sigma), Methanol, ethanol, 1-propanol, and distilled water. While for synthesis PEEK, the materials includes toluene , 4,4-Difluorobenzophenone, hydroquinone and potassium carbonate (K2CO3). Solvent that were used as a dispersing arents are Sulfolane, Dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF). 2.2 Characterization 2.2.1 Thermogravimetry analysis The effect of fillers on the thermal stability of the polymer composites was performed using Thermogravimetry analysis (TGA) by METTLER TOLEDO with nitrogen flow at 40 ml min-1. The samples were heated from room temperature until 800oC at a rate of 10oC min-1. 5-10mg of sample weight was taken to analyze and aluminium pan were used in this analysis. 2.2.2 Differential Scanning Calorimeter Melting and crystallization properties of PEEK in the presence of alumina nanofiber were determined by DSC. Aluminium pan were heated from 50oC to 800oC at a 10oC min-1 of heating rate. At 400oC, the process was isothermally for 5 minutes in order to let the polymer completely melt. Then, the samples were cooled to 50oC at a rate of 10oC min-1 . 2.2.3 Transmission Electron Microscopy Investigation on the dispersion and homogeneity of the filler within the PEEK matrix were observed by Transmission electron Microscopy (Philips. Solvent like ethanol was used to solute the sample and placed it onto the carbon grid for viewing. Before viewing, carbon grid have to be completely dry in order to get a quality micrograph. 2.2.4 Fourier Transform Infrared IR spectra were recorded on PERKIN ELMER in identifying the functional group of the PEEK with the Alumina nanofiber. Solid sample were grouned with dry Potassium Bromide (KBr)

until well mixed. Then the mixture was pressed into a transparent thin disk in an evacuable die at sufficient pressure before being analyzed.

2.3 Synthesizing of Alumina Nanofiber with PEEK The nanocomposite were prepared by preparing the alumina nanofiber by sol gel method. Firstly, aluminium isopropoxide was hydrolyzed in distilled water and 1-propanol under vigorous stirring for 24 hours. Then the mixture was age for 72hours at room temperature. The suspended solid was filtered using filter flask and vacuum pump by suction filtration. Rinsed thoroughly the filtered product using ethanol and dried at ambient temperature. For the last steps, it was calcined at 540oc for 5 hours in air. Then alumina nanofiber loading from 1%, 2.5% and 5% was sonicated in 15 ml of solvent using ultrasonic bath (W) for 30 minutes. Then, the mixture will placed in three necked flask with 0.66g of Hydroquinone, 1.31 g of 4, 4- difluorobenzophenone, 1.24 g of K2CO3 and 35ml toluene. The flask was fitted with Dean-Stark trap, condenser, mechanical stirrer and nitrogen inlet and was set inside conventional microwave (Samsung, maximum power 700W, 2455MHz). The polymerization occur under nitrogen atmosphere and continous stirring (300rpm). The reaction mixture was heated under reflux at 80-110 oC for 20 minutes and distilled of the water that produce by azeotropic distillation. Then, the temperature was increased until 110 oC to 130 oC for 15min and distilled off the toluene. After that, the reaction was maintained at 180 oC to 200 oC for 5 minutes . the reaction was cooled until room temperature and precipitate with distilled water. Refluxed the product with water and filter the polymer before proceed with Soxhlet extraction using methanol to purified it. Lastly, the polymer that obtained was dried under vacuum at 100 oC for 24hours. 3. Results and Discussions 3.1 Dispersion of Alumina nanofibers in PEEK matrix Figure 1shows TEM images of alumina nanofibers dispersed within the PEEK matrix. From the micrograph it can be observed that the fiber are long with the range of diameter of 2nm to 9nm. As shown in figure 2, the alumina nanofiber diameters mostly 2-6 nm of the alumina nanofiber size the tabulated of nanofiber size presence. The alumina nanofibers were dispersed in a solvent by ultrasonication for 30 minutes in order to achieve well dipersion and good distribution of the fibers. As can be seen in figure 1, the fibers were dispersed homogenously after sonicated for 30 minutes although some of them were overlapping to each other. Nanoscale fillers tend to stick together compare to the microfillers. It is due to hydrophilic force around the fibers. [2]. It proved that by sonication and proper dispersion medium, well dispersion and homogenous of fillers can be achieved.

Figure 2: dispersion of alumina nanofiber in PEEK at 100nm and 50nm


Thermal degradation of PEEK-Alumina Nanofiber

Figure 3: TGA/DTG curves of (a) PEEK, (b) PEEK-1% Alumina Nanofiber, (c) PEEK-2.5 % Alumina Nanofiber and (d) PEEK-5% Alumina Nanofiber.

TGA was performed to investigate the thermal stability of the nanocomposites. TGA curves of PEEK with loading 1%, 2.5% and 5% weight fraction of alumina nanofiber are presented in figure 2. Decomposition of PEEK and its composites proceeds in nitrogen environment. The effect of alumina nanofiber were studied by comparing the degradation temperature (Td) and char yield of the polymer nanocomposite with the synthesized reference PEEK. The summarization of the comparison results for the PEEk and composites are tabulated in table 1.

Sample PEEK PEEK + 1%Alumina Nanofiber PEEK + 2.5%Alumina Nanofiber PEEK + 5%Alumina Nanofiber

Degradation temperature (oC) T10 412 405 397 222 T25 442 572 529 555 T35 452 517 592 638

Char Yield % at 800 oC 48.78 53.38 78.20 59.70

Table 1: Degradation temperature (Td) of polymer composites at 10 wt%, 25 wt% and 35 wt% loss and their char residue.

The onset temperature at 10% of weight losses is decreased for 1%, 2.5% and 5% of alumina nanofiber loading compare to PEEK. While at 25% and 35% of weight losses, the degradation temperature are arise with the increasing of alumina nanofiber loading to the PEEK. Another observation that noted in this case, there are two steps in the degradation temperature for PEEK

with 2.5% and 5% of alumina nanofiber shown by two peak appear in DTG curve . Yin et al identified that only one step of weight losses of pure PEEK at 607 oC observe that assigned to the pyrolisis of the polymer [5]. It has been proposed that decomposition of PEEK involving a few mechanisms. The composite were decomposed in two steps. For the first decomposition step, it attribute to the random chain scission of the ether and ketone bonds [20]. For composites, there were steps below 100oC. This may be due to physically adsorbed water and organic molecules from alumina nanofiber [1]. The weight loss rapidly occurs below 600oC and it become stable until 800oC. The residue from the decomposition appears to be a carbonaceous char [1]. Besides, there are reported that over this temperature range, CO and CO2 to be produce rapidly. [22] Table 2 shows that the presence of the alumina nanofiber in the PEEK has been stabilize the polymer with the high yields residue at 800oC from 48% to 53.78%, 78.20% and 59.70% respectively.This is mainly attributing to the strong interaction between the alumina nanofibers and the PEEK matrix and proved that the polymer composites has improved the thermal stability. Kashiwagi and Yang reported the similar trend of thermal degradation behavior in preparing CNT with the polymer. FTIR


1650 1645 1494 1300

Figure 2: IR spectra of PEEK with alumina nanofiber loading.

Figure 2 shows the infrared spectrum of the polymer nanocomposites. The effects of the presence alumina nanofiber to the chemical bonding of PEEK were studied. In this case, we just focus on the band in the region 3500cm-1 to 1300cm-1 which are the main functional group that appear for PEEK. A weak band obviously appeared at 3400 cm-1 that shows the existence of hydroxyl group. The absorbance of the band raised and shifted to higher frequency with the increasing of the alumina nanofiber loading due to the stretching vibration of isolated hydroxyl groups that involved in hydrogen bonding [31]. A strong absorption band in the region around 1645 cm-1 is due to C=O stretching and the presence of this band points carbonyl group. The band seemed to be broaden to lower frequency with higher alumina nanofiber loading. While, the absorbance for carbonyl group become higher after the PEEK loading with alumina nanofiber. On the other hand, C=C stretching bands for aromatic rings usually appear in pair between 1600 and 1475 cm-1. Similar trends were observed in the spectra that the aromatic rings stretching frequency at around 1600 cm-1 and 1494 cm-1. The introduction of the alumina nanofiber into the PEEK shifted the both band for aromatic group to the higher frequency. The shifting was effected by electron withdrawing, indicating that the bonding for C=C become stronger because of the increasing double character. At 1300 cm-1 ether give strong C-O-C absorption in this region for PEEK loading with 1%, 2.5% and 5% wt of alumina nanofiber. The infrared absorption band of PEEK synthesized with alumina nanofiber shows the different derivatives of intensity from the unmodified PEEK indicating the interaction of inorganic filler and organic compound. Ellis et al state that, IR spectra of semicrystalline polymer shows two carbonyl stretching vibration at 1648 cm-1 and 1655 cm-1 which because of the crystalline and amorphous phase of the polymer and its similarly shows in the figure 2. The small change could be due to the different level of crystallinity properties of the polymer nanocomposites [4].


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