Jurnal Teknologi Proses Media Publikasi Karya Ilmiah Teknik Kimia
6(1) Januari 2007: 82 – 84 ISSN 1412-7814
The Thermal Properties of Calcium Carbonate Filled Polypropylene (PP)/ Ethylene Propylene Diene Terpolymer (EPDM) Composites Salmah Department of Chemical Engineering, Faculty of Engineering University of Sumatera Utara, Medan 20155 Abstract The thermal and crystallization behavior of PP/EPDM/CaCO3 composites was studied by thermogravimetry analysis (TGA) and differential scanning calorimetric (DSC). The results showed that the increasing of filler loading increase the thermal stability and crystallinity of PP/EPDM/CaCO3 composites. Keywords: paper sludge, calcium carbonate, polypropylene, ethylene propylene diene terpolymer, composites.
Introduction
Thermal analysis of polymers is an important subject as it covers a broad field, ranging from the development of thermoresistant polymers and ablation problem to the stabilization of thermolabile polymers. Thermal analysis is an important analytical method in understanding the structure-property relationship and mastering the technology for molecule design and industrial production of different polymeric materials. Moreover, it is a useful technique to determine the thermal stability of the materials. In addition, it is possible to quantify the amount of moisture and volatiles present which can cause detemoration in the composites.
thermogravimetry (TG). Thermogravimetric data indicate a number of stages of thermal breakdown, weight loss of the material in each stage. Threshold temperature, etc. Both TG and derivative thermogravimetry (DTG) will provide information about the nature and extent of degradation of material. In differential scanning calorimetry (DSC), the heat flow rate associated with a thermal event can be measured as a function of time and temperature allowing us to obtain quantitative information about malting and phase transition of the composite system. Experimental Materials
Thermal analysis studies have been carried out and the effects of crystallinity, orientation and cross-linking haven reported (Daniel et al., 1994, George et al., 2000, Fangling et al., 2004, Joseph et al., 2003). One of the accepted methods for studying the thermal properties of polymeric materials is
Polypropylene homopolymer used in this study was of injection molding grade, from Titan PP polymers (M) Sdn Bhd, Johor, Malaysia (code 6331) with MFI value of 14.0 g/10 min at 2300C. Ethylene propylene diene monomer, grade Mitsui EPT 3072 E was obtained from Luxchem Trading Sdn Bhd.,
Salmah / Jurnal Teknologi Proses 6(1) Januari 2007: 82 – 84
Selangor, Malaysia. Calcium carbonate was obtained from Malaysia Calcium Corporation Sdn Bhd., Malaysia, with average size of 4.5µm (density, 2.7 g/cm3). The formulation of PP/EPDM/CaCO3 composites used in this study is shown in Table 1. Tables 2 show the results of semi-quantitative analysis of calcium carbonate used in this study. Mixing Procedure
Composites were prepared in a Haake Reomix PolyDrive. Mixing was done at 180 0C and 50 rpm. EPDM was first charged to start the melt mixing. After 3 min. filler was added followed by PP at the fifth minutes. Mixing was continued for another 5 min. At the end of 10 min, the composites were taken out and sheeted through a laboratory mill at 2.0 mm nip setting. Sample of composites were compression molded in an electrically heated hydraulic press. Hot-press procedures involved preheating at 180 0C for 6 min followed by compressing for 4 min at the same temperature and subsequent cooling under pressure for 4 min.
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perfectly (100%) crystalline PP, respectively. For UHof (PP) a value of 209 J/g was used for 100% crystalline PP homopolymer (Greco et al., 1987). Xcom, which is calculated using this equation, however, gives only the overall crystallinity of the composites based on the total weight of composites including noncrystalline fractions, and it is not the true crystallinity of the PP phase. The value of crystallinity for PP phase (Xpp) of the PP fraction was normalized using Eq. (2) as follow (Shoinake et al., 1998): Xpp = (Xcom)/Wfpp
… (2)
Where Wf pp is the weight fraction of PP in the composites. TABLE 1: Formulation of PP/EPDM/CaCO3 composites with different filler loading Materials Composites Polypropylene (PP) (wt %) 50 EPDM (wt %) 50 Calcium carbonate (wt %) 0, 15, 30, 45, 60
Thermogravimetry Analysis
Thermogravimetry analysis of the composites was carried out with a Perkin Elmer Pyris 6 TGA analyzer. The samples weight of about 15 – 25 mg were scanned from 50 to 600 0 C using a nitrogen air flow of 50 ml/min and a heating rate of 20 0C/min. The sample size was kept nearly the same for all tests. Differential Scanning Calorimetry
Thermal analysis measurements of selected systems were performed using a Perkin Elmer DSC-7 analyzer. Samples of about 10 – 25 mg were heated from 20 to 220 0C using a nitrogen air flow of 50 ml/min and the heating rate of 20 0 C/min. The melting and crystallization behavior of selected composites were also performed using a Perkin Elmer DSC-7. The crystallinity (Xcom) of composites were determined using the following relationship: Xcom (%cryst) = UHf/UHof x 100
… (1)
Where UHf and UHof are enthalpy of fusion of the system and enthalpy of fusion of
Results and Discussion
Thermogravimetry analysis (TGA) curve of PP/EPDM and PP/EPDM/CaCO3 at 0,30 and 60 wt % filler loading is show in Figure 1. Table 3 show that the end degradation temperature (Te deg) and total weight loss of PP/EPDM/CaCO3 at different filler loading. The total weight loss of PP/EPDM/CaCO3 composites at 60 wt% is lower than PP/EPDM/CaCO3 at 30% and PP/EPDM, which might be due to the presence of large content of inorganic material in CaCO3 with increasing filler loading. This result indicate that PP/EPDM/CaCO3 composite have better thermal stability compared PP/EPDM. TABLE 2: Semi quantitative analysis of Calcium Carbonate using X- Ray Flourescene Spectrometer Rigaku RIX 3000. Component Wt % CaO 56 MgO 1 0.13 SiO2 Al2O3 0.072 Fe2O3 0.019
Salmah / Jurnal Teknologi Proses 6(1) Januari 2007: 82 – 84
84 Component P2O5 SrO SO3 LOI
TABLE 4: Parameter DSC of PP/EPDM/CaCO3 composites with different filler loading.
Wt % 0.016 0.015 0.011 42
Composites
TABLE 3: Percentage weight loss of PP/EPDM/CaCO3 composites with different filler loading Composites Te deg (0C) Total weight loss (%) PP/EPDM: 50/50 587.2 100 PP/EPDM/CaCO3: 587.6 79.2 50/50/30 PP/EPDM/CaCO3: 587.9 69.4 50/50/30
Table 4 show the parameter differential scanning calorimetric (DSC) of PP/EPDM/CaCO3 at different filler loading. The value of melting temperature (Tm), heat of fusion of composites (UHf (com)), crystallinity of composites (Xcom) and crystallinity of PP (Xpp) also show in Table 2. The results show that the percentage of crystallinity of composites changed with filler loading. It can be seen that the value of UHf(com) and Xcom decrease with increasing filler loading. This is due to the decreasing of PP content at higher filler loading. The addition of fillers results in an increase in Xpp. This behavior is consistent with the results by reported by Salmah et al., (2005). 110
weight loss (%)
90 70 50 30 PP/EPDM : 50/50
10
PP/EPDM /CaCO: 50/50/30 PP/EPDM /CaCO3: 50/50/60
-10 50
250
450
650
Tem perature ( 0C)
FIGURE 1: Thermogravimetric analysis (TGA) curve of PP/EPDM/CaCO3 composites at 0, 30 and 60 wt % calcium carbonate.
PP/EPDM/: 50/50 PP/EPDM/ CaCO3: 50/50/30 PP/EPDM/ CaCO3: 50/50/60
Melting temperature
Hf (com)
Xcom
Xpp
Tm (0C)
J/g
(% crystallinity)
(%)
167.1
40.07
19.2
38.4
162.5
34.85
13.9
39.4
162.4
28.85
12.5
40.3
References Daniel, T. Q., Yin, M., James, A. K., Caufield, D. F. 1994. Crystallinity in the polypropylene/cellulose system. II. rystalliation kinetics. Journal of Applied Polymer Science. 52, 605-615. George, S., Varughese, K. T., Thomas, S. 2000. Thermal and cryatallisation behavior of isotactic polypropylene/nitrile rubber blends. Polymer, 41, 5485-5503. Gong, F., Feng, M., Zhao, C., Zhang, S., Yang, M. 2004. Thermal properties of poly (vinyl chloride)/montmorillonite nano-composites. Polymer degradation and stability. 84, 289294. Joseph, P. V., Joseph, K., Thomas, S., Pillai, C. K. S., Prasad, V. S., Greoninckx, G. 2003. The thermal and crystallization studies of short sisal fibre reinforced polypropylene composites. Composites Part A: applied science and manufacturing. 34, 253-266. Greco R., Manacarella C., Martuscelli E., Ragosta G. 1987. Polyolefin Blends: 2. Effect of EPR composition on Structure, Morphology and Mechanical Properties of iPP/EPR Alloys, Polymer, 28: 1929- 1936. Salmah., Ismail, H & Abu Bakar, A. 2005. A comparative study on the effects of paper sludge and kaolin on properties of polypropylene/ethylene propylene diene terpolymer composites. Iranian Polymer Journal. 14 (8), 705-713. Shoinaike, G. O., Kiat, T. H. 1998. Studies on miscibility of uncompatibilized nylon 66santoprene blends. J. Appl. Polym. Sci., 68: 1285-1295.
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ω ρ μ
diameter dalam kolom (cm) bilangan Reynolds osilasi frekuensi sudut (rad/s) densitas fluida (kg/m3) viskositas fluida (kg/m.s)
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… Rujukan … Setiap rujukan harus disertakan sumbernya seperti contoh berikut:
100 Vf 0 l/min, 2214
Fb0 (cm 3/s)
80
3 cm 5 cm
60
40
20
0 0
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D Reo
0.4
0.8 1.2 x o* f (cm/s)
1.6
2
GAMBAR 1: Pengaruh diameter bukaan pada keadaan tanpa aliran kehadapan. (TNR 10 pt)
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… Tata Nama … kecepatan antar muka (cm/s) u0 v viskositas kinematik (m2/s) amplitudo osilasi (cm) x0
1. … model Peringkat Unggul dengan Pencampuran Balik (Ideal Stage with Backmixing Model, ISB) dikembangkan oleh Xu (1994) dan Mohd. Sobri Takriff (1996). 2. … dengan menggunakan ISB model (Xu 1994; Mohd. Sobri Takriff 1996). 3. … kajian fenomena pencampuran balik di dalam kolom bersekat (Howes & Mackley 1990; Zuhrina Masyithah & Mohd Sobri Takriff 2000a, 2000b). …
… Daftar Pustaka
… (contoh rujukan jurnal) Howes, T. & Mackley, M.R. 1990. Experimental axial dispersion for oscillatory flow trough a baffled tube. Chem.Eng.Sci. 45: 1349-1358. (TNR 10pt) (contoh rujukan prosiding & tahun terbit yang sama) Zuhrina Masyithah & Mohd Sobri Takriff. 2000a. Interstage backmixing in oscillatory flow in a baffled column. Proc. 2nd International Conference on Advances in Strategic Technologies. 1: 493-498. Zuhrina Masyithah & Mohd Sobri Takriff. 2000b. Interstage backmixing in oscillatory flow in a baffled column. Jurnal Teknik Mesin. 3(1): 55-60. (contoh rujukan buku teks) Fogler, H.S. 1992. Elements of chemical reaction engineering. Ed.2. New Jersey: Prentice-Hall. (contoh rujukan skripsi/tesis/disertasi) Mohd Sobri Takriff. 1996. Column flooding, gas holdup and interstage backmixing in an aerated multistage, mechanically-agitated, compartmented column. Ph.D Dissertation. University of Arkansas. (contoh rujukan internet) Elsevier. 2002. Pedoman penulisan kertas kerja. http://www.elsevier.com (26 Agustus 2002). (catatan: 26 Agustus 2002 adalah tanggal saat situs tersebut dirujuk).
