Mechanical Properties and Microstructures of Exfoliated Graphite Nano Platelet Reinforced Thermoplastic Nanocomposites H. JUNAEDI’, A. A. ALMAJID*? and K. FRIEDRICH?* TRACT Exfoliated graphite nano platelets (EG) were fabricated and processed with high density polyethylene (HDPE) to produce EG/HDPE composites. Different compositions of EG/HDPE were prepared: 0%, 1%, 2.5%, and 5% weight of EG. The mechanical properties and microstructures of the composites were investigated EG was fabricated using natural flake graphite (NFG) with 300um diameter size. NFG was then intercalated using a Perchloric Acid and Potassium Permanganate (KMn0,) system. The intercalated graphite was expanded at 800°C, and then was sonicated for 6 hours. The produced exfoliated graphite possessed a mean diameter of 38.5um and a thickness of around ISnm. It was called EGI. As- received and ball-milled EG with mean diameters of 94m and 2m and thicknesses of 8nm and 4nm, respectively, were also used, designated as EG2 and EG3 EG and HDPE were pre-mixed by a mechanical disperser in the presence of an isopropyl alcohol (IPA) solvent and then dried. EG/HDPE composites were then fabricated using a twin-screw extruder, followed by injection molding. Hardness, tensile and impact tests were carried out to evaluate the performance of these composites 5% EGI increased the tensile modulus of elasticity of the EG/HDPE composite by 24% and the yield stress by 5.5%. The ultimate tensile strength, on the other hand, experienced a reduction of 47%. A bigger particle sized EGI resulted in a higher increase of the tensile modulus in a 1% EG loading compound, compared to EG2 and EG3. EG3 with the smallest particle size showed lower tensile properties, due to an EG agglomeration in the HDPE Matrix. The hardness exhibited no changes in all composition, whereas impact strength decreased in general. Department of Mechanical Engineering, College of Engineering, King Saud University, Saudi Arabia “Center of Excellent in Research of Engineering Materials (CEREM), King Saud University, Saudi Arabia “institute for Composite Material, (IVW), Technical University of Kaiserslautern, Kaiserslautern, Germany 297INTRODUCTION Polymers, in general, have limited mechanical properties when compared to metals. Therefore, a modification of polymers using nanoscale filler particles has found an increasing attention recently [1-5], because it that can improve the mechanical, thermal, optical and electrical properties of a polymeric material in addition to cost savings. Polymers can be modified with metallic and metal oxide (ceramic) fillers for more specific uses such as corrosion resistant paints, electronic devices, sensors, rechargeable batteries, etc. The properties of polymeric composites depend upon the concentration of filler, its size and shape, distribution or orientation of filler, the state of aggregation and agglomeration, matrix morphology and so on Nano-reinforcements, especially exfoliated graphite nano-platelets (EG), have been under investigation in the Drzal and other groups [5-9]. This nano material is a potential alternative to clays and carbon nano tubes since EG reinforced polymer nanocomposites have good mechanical properties, even if they have only a low EG content of less than 2 vol%. Use of graphite nano-platelets as fillers to produce graphite reinforced polymer nanocomposites has also a cost advantage as well as other superior physical properties ‘There are several classifications of polyethylene but three types are of special interest, namely LLDPE (Linear Low Density Polyethylene), LDPE (Low Density Polyethylene), and HDPE (High Density Polyethylene). Each type has a different specification and application. LLDPE is used for cable covering, toys, lids, buckets, containers and pipes. LDPE is used for plastic bags and film wraps, whereas HDPE is used for packaging, water pipes and garbage containers In the current research we will study the effect of chemical composition and particle size on the microstructure and the mechanical properties of exfoliated graphite nano-plateleyHDPE composites MATERIALS AND EXPERIMENTAL PROCEDURE Materials Natural flake graphite (NFG) with 300m diameter size and as-received exfoliated graphite, supplied from Asbury Carbon, were used as basic reinforcements. Intercalation of the graphite was performed by using 70% perchloric acid (PA) 70% as the intercalation solvent and potassium permanganate (KMn0,) as the oxidizer. High density polyethylene (HDPE) of type F00952 from SABIC in pellets form was used as the matrix material. The melt processing temperature was supposed to be between 200-235°C, and the melt flow rate of this HDPE amounted to 0.05 g/l0min at 190°C and 2.16 kg, according to the data sheet of the producer 298TABLE I. COMPOSITION OF COMPOSITES. Material No. | T#2No. | Compositions 1) HDPEI Neat HDPE 2 | HDPED | HDPE+ 1% BGI 3 | HDPES | HDPE +25%EGI a_| HDPET 3 | HDPES I%EGI 6 | HDPE6 | HDPE + 1% BGs FABRICATION OF EXFOLIATED GRAPHITE An experimental design was made to determine the best ratio between natural flake graphite, perchloric acid, KMnO,, and intercalation time ‘The expansion process was carried out at 800°C, with a heating time of 20s After this process, the expanded graphite was mixed with acetone and sonicated for 5 hours, followed by drying in an oven at 90°C to get exfoliated graphite (called EGI). For comparison, as-received EG was also used (called EG2). Furthermore, as- received EG was ball-milled for 20h by using a Pulverisette 7 from Fritsch in order to get a smaller EG size (called EG3). FABRICATION OF COMPOSITES ‘The content of exfoliated graphite nanoplatelets in the composites was chosen to be 0, 1, 2.5 and 5% by weight. Each composition (Table I) was dispersed in isopropyl alcohol (IPA) and then mechanically mixed using a milling disperser mixer, After that, IPA was evaporated resulting in HPDE with different amounts of EG inclusions. The latter materials were then melt-mixed by a twin-screw extruder (Brabender 828401) at a temperature of 223°C in order of form composite pellets. They could be formed into specimens by injection molding machine (Arburg 221K All Rounder 350-100) at a temperature of 240°C, CHARACTERIZATION OF THE EG’S AND THE COMPOSITES The particle sizes of the as-produced exfoliated graphite nanoplatelets were measured using a particle size analyzer (PSA), Mastersizer 2000, Malvern Thickness calculations of the various EGs were based on observation by transmission electron microscopy (TEM 2100F from JEOUL). Additional structural details of EG were determined by X-Ray diffraction (XRD). Tensile properties of the composites were measured at room temperature in an INSTRON universal testing machine, using a cross-head speed of 50 mm/min, For each material, at least three tensile specimens taken from the same composition 299were tested. Hardness values of the composites were measured by a Durometer (Shore D), with five readings from each material. Impact tests were also carried out at room temperature, using an Izod impact tester from CEAST. The microstructure of the composites was analyzed by using a field emission scanning electron microscope (FESEM), type JSM 7600F, from JEOUL- RESULTS & DISCUSSION Filler Size Distribution ‘The mean diameter of the self-made EG! amounted to 38.5 ym, the one of the as-received EG2 9.2 um, and of the ball-milled EG3 22 um (Figure I to 3, and Table II) 1 ue Figure |. Size distibution of E platelets votre) arte Sze (un aa RET Figure 2. Size distibution of EG2 platelets, rt Se sn aa ea eT Figure 3. Size distribution of EG3 platelets 300TABLE II. TABLE OF PARTICLE SIZE DISTRIBUTION OF EXFOLIATED GRAPHITE. Tag No. 410%) | 460%) | 40%) | dmean EGI | 13:52pm | 33409um | 704m | 38487 pm EG? | 2779am | 7-502um [17 772um | 9176um EG) | 0363um | 1766um | 4441um | 2179nm (002) Shes = GNP2 Intensity (CPS) Figure 4. XRD result of EG1, EG2, and EGS. XRD OF EXFOLIATED GRAPHITE Figure 4 shows the XRD results for the EG’s with different diameter size. The (002) peak for EG1, EG2, and EG3 can be found at 26.52°, 26.38", and 261°, respectively. There is onily a slight peak shifting for all three different sizes. But itis more remarkable that a smaller diameter size gives a lower peak height, TEM OF EXFOLIATED GRAPHITE Figure 5(a) shows the thickness of platelets EGI, Their thickness is around 15nm. The exfoliation procedure in combination with the sonication process could produce nano-thickness graphite with a large platelet diameter. Figure 5(b) represents the thickness of platelets EG2 and the corresponding distances between the graphene layers inside the platelets. The thickness of this platelet is around 8nm and the distance between the layers amount to 0.34nm. Ball milling (Figure 5(c)) reduces the thickness of EG3 platelets down to 4.35nm, but remains the distance between graphene layers at about 0.35nm. The diameter of the EG2 was um, and after ball-milled reduced to 2 um. So, ball-milling is able to reduce the diameter of EG’s but also their thickness 301Rau Ree Figure 5. TEM image of (a) EGI, (6) EG2, and (c) EG3. MICROSTRUCTURES OF THE COMPOSITE Far Figure 6 shows the fractured surfaces of the neat HDPE and its composites. All specimens were broken at a temperature of -196 °C. The surface of HDPE (Figure 6 (a)) is relatively smooth since no particles are embedded in it. This image will be used as a comparison with the composites 302The latter possess for all compositions a more contoured surface, in which a good dispersion of the EGs is visible. The platelets embedded in the HDPE matrix were randomly oriented, i.e. from parallel to perpendicular to the fracture surface. TENSILE PROPERTIES The results of the mechanical tests for the pure HDPE and its composites are summarized in Table III. In general, the tensile strength of the composites increased compared to the pure HDPE matrix material. The composite containing Swt% of exfoliated graphite has the maximum tensile modulus and yield strength. Pyne Figure 6, FESEM image of (a) the neat HDPE (HDPE1), (b)HDPE2, (c) HDPE3, (@) HDPE, HDPES, and (f) HDPE6, fracture surface 303‘TABLE II MECHANICAL PROPERTIES OF THE COMPOSITES, rag | Tewsile | Viel | TREE | og rain | Hates | Impact Fee | modulus | sess | Jemile | % Stain | “(shore | od ara) | vrs | Sire Dd) | dim 1134 178 32.6 253 63.6 101A 1393] 187 336 9 | 4] 61.36 127 | 184 332 153 | @8 | 6954 1409 | _188 311 199 | 642_| 4982 (ares | —1192—[ 19.4 368 Ta 64a] 9353 (apps | m7 177 336 209] 640] 97:36 Figure 7 (left) illustrates a comparison of different wt% of EGI in HDPE matrix. The modulus increases by up to 24% for 5% of EG1 loading, compared to the neat HDPE, Figure 7 (right) demonstrates the effect of the platelet dimensions on the modulus of elasticity at 1% loading. A smaller platelet size tends to decrease the improvement of the modulus value. 1 wt% of EGI (HDPE2) result in a 14% increase, whereas 1 wt% of EG2 gives only a slight enhancement (HDPES). The addition of 1 wi% of EG3 does not change modulus value at all Additional effects of the EG filler on the yield stress are shown in Figure 8 (left). It seems that there is a minimal improvement by the addition of EG for all compositions. These might be due to a reduced mobility of the polymer chains on plastic deformation under the presence of the EG fillers, ‘When it comes to the effect of EG filler dimensions on the yield stress, the differences at Iwt% loading are also very limited. The best results were observed for HDPES Figure 8 (right). Figure 9 (left) shows the ultimate tensile strength (UTS) as a function of EG wt%. A wide range of standard deviations for HDPE2 and HDPE3 informs that the dispersion of the EG is not uniform within the specimens. A similar inconsistency is also visible for the composites with different platelet dimensions, but the same filler content (Figure 9 (right)) Regarding the strain at break, it can be considered, in general, that an addition of EG to an HDPE matrix reduces this property (Figure 10 (left)). However, once the platelets are in there, it seems that a higher wt% of EG tends to give a bit of improvement. So, there is a competition between enhancement and weakening Weakening is probably due to a filler agglomeration and a perpendicular filler orientation relative to the loading direction. The enhancement, on the other hand, may come from a filler atrangement parallel to the loading axis. An increase in quantity of EG tends to arrange more platelets parallel to the injection molding and loading direction, as it usually occurs in short fiber reinforced thermoplastic composite [10], A similar tendency is seen, when the neat HDPE is compared with the lw% EG filled system (Figure 10 (right)). Here, the system with the smallest filler dimensions (HDPE6) is better than the two other nanocomposites, but still lower than the HDPE matrix. It is assumed that due to their smaller platelet size, EG3 is more uniformly distributed than the large EG1 or EG2 platelet. In this way they may cause less sites of local stress concentration in the polymer matrix. 304yy ‘deena 0) eBERe Gabe Torte oa Pa) oRR St bb aa Composten Compaston Figure 7, Effect of wt% of EG (left), and platelet dimensions of Iwt% of EG (right) ‘on tensile modulus of elasticity of composites, Ya Ss 049 ieee eee f wt% of EG (left), and platelet dimensions of 1 wt% EG (right) on the yield stress of composites. SS \G Ly urs) \S Figure 9. Effect of EG wt % (left), and platelet dimensions of lwt% of EG ‘on the ulimate tensile strength of composites, I. % Sean area 6 gta ata eee eureFigure 10, Effect of wt % of EG (left) and platelet dimensions of Iwt% of EG (right) ‘on the strain at break of composites. F EA «. E 1 | | 3° i | ie : | | 2° is YA is a Wy aS i UZ : ‘Composition ‘Compostinn i: Figure 11 Influence of EG wt % (eft) and platelet dimension of Iwt% of EG (ight), on the hardness of HDPE nanocomposites. ES EE Pr yy, es _ ue Ve asi Za Pel | VF PA) 77 Es | | | Ball || IZA WF 2 | Sta Sens Figure 12. Bifect of BG wi (eft) and platelet dimensions of Iw of EG (ih, on the Izod impact energy of HDPE nanocomposites. HARDNESS Hardness values of the composites show a different trend than the tensile modulus and strength. There is almost no difference in hardness between the pure HDPE and all the composites. It exhibits that the properties do not change on the micro-scale due to the very small amount of EG inside of the bulk material (Figure 1), IZOD IMPACT ENERGY A similar tendency as observed for the strain to failure is also detected for the Izod impact energy (Figure 12). There is only one exception, i.e. HDPE4 in Figure 12 (left), as it seems that these measurements must be repeated. The reasons for these tendencies were already described before and hold also for the impact behavior. In case the platelets are oriented parallel to the injection molding direction of the sample, they act as transverse barriers when fracture take place under a bending load, as it occurs in the Izod impact testing. In this way they can bridge the crack as it was observed previously [11] 306CONCLUSION HDPE composites reinforced with exfoliated graphite nanoplatelets have been successfully prepared by twin-screw extrusion, followed up by injection molding The addition of these fillers resulted in different changes of properties. From this research the following conclusions can be drawn: 1. The tensile modulus of elasticity increased by 24% when adding 5 w1% of EG to the HDPE matrix. The yield stress increased also by 5.5 %, whereas a decrease of 4.7% was observed for the ultimate tensile strength. The bigger platelet dimension of EGI resulted in a higher increase of the tensile modulus at 1wt% EG loading compared to EG2 and EG3 In general, the UTS values are rather inconsistent, i.e, no clear tendency is visible But it must also be mentioned that the differences measured in this property are on a very similar level and fall within the larger scatter bars found for materials HDPE2 and HDPE3 3. Strains at break decreased by the addition of EG, but this general reduction became less once the EG content increased. Smaller particle size also resulted in a smaller deterioration of the strain at break 4. The surface hardness did not change at all by the addition of EG up to 5w1% This means, the surface properties on the micro-scale are not affected by the very small amount of EG inside the bulk 5. 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