Waste polyethylene (PE) bags were reused in the modification of commercially available bitumen. The bitumen/PE blend was prepared by mixing homogenously commercial bitumen with waste PE in the molten state. The samples of bitumen blend and bitumen base were rheologically analyzied. The rheological properties such as complex modulus, shear compliance, torque and complex viscosity of bitumen and bitumen blend were studied using an ARES- Rheometer (Rheometric Scientific, Co.) in the dynamic mode, plate-plate geometry with diameter 8 mm. The measurements were performed over a wide range of temperatures ranged from-10°C to 60°C and frequencies from 100 to 0.1 radians per second. The results evidence that the complex modulus, shear compliance, torque and viscosity are improved by the incorporation of the waste PE into bitumen. The flow activation energy for neat bitumen and bitumen-9%PE are calculated from 0 by using the rheometric software.

Philosophy

International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  1 Rheological Characterization of Bitumen/Waste Polyethylene Composites: Part III Mahmoud Abdel-Halim Abdel-Goad Chemical Engineering Dept., Faculty of Engineering, Minia University, Egypt (E-mail:) Abstract- Waste polyethylene (PE) bags were reused in the modification of commercially available bitumen. The bitumen/PE blend was prepared by mixing homogenously commercial bitumen with waste PE in the molten state. The samples of bitumen blend and bitumen base were rheologically analyzied. The rheological properties such as complex modulus, shear compliance, torque and complex viscosity of bitumen and bitumen blend were studied using an ARESRheometer (Rheometric Scientific, Co.) in the dynamic mode, plate-plate geometry with diameter 8 mm. The measurements were performed over a wide range of temperatures ranged from-10°C to 60°C and frequencies from 100 to 0.1 radians per second. The results evidence that the complex modulus, shear compliance, torque and viscosity are improved by the incorporation of the waste PE into bitumen. The flow activation energy for neat bitumen and bitumen-9%PE are calculated from 0 by using the rheometric software. Keywords: bitumen; rheology; polymer modification, waste plastics. 1. INTRODUCTION Bitumen is the black adhesive that binds flexible pavements on roads and airfields together. Bitumen is also used in other areas of application, such as waterproofing, flooring and joint materials. Almost all bitumen originates from crude oil and is the residue of a refining process. It is well-known that bitumen is a very complex and temperature dependent material consisting of hydrocarbon molecules. Naphtenic-base crude oils often give a large yield of bitumen that may be of good quality, while paraffinic crude oils may give bitumen of good quality or yield bitumen not suitable for road construction [1]. Nowadays a very large majority of the roads are constructed using a mixture of bitumen (5 wt %) and mineral aggregates. Notwithstanding this low bitumen content, the performance of the road pavement depends to a large extent on the properties of bitumen itself, since it constitutes the only deformable component. The correlation between the complex colloidal structure of bitumen and its viscoelastic response is therefore a subject of scientific and technical interest [2 -7]. Polymer additives are well-known to improve the rheological properties of bitumen The polymer addition allows an increase in the resistance of the binder to permanent deformation at high temperature.Besides, the fracture properties including critical stress intensity factor (K1C) at low temperature of polymer modified bitumens (PmB's) were shown to be higher than those of the bitumen base.To determine the crack propagation mechanism controlling fracture properties, previous studies have focused on establishing the relationship between the fracture properties and the morphology of polymer modified bitumen [8] The addition of synthetic polymers to enhance service properties over a wide range of temperatures in road paving applications was considered a long time ago and nowadays has become a real alternative. As has been pointed out in relevant papers about bitumen and polymer/ bitumen blends[9 -18 ] understanding the interactions of asphaltene and maltene (main components of bitumen) with the polymer, is a crucial point to gain insight into the routes to improve the capacities of these systems. In recent years, the volume of municipal plastic waste (MPW) has increased greatly, and this has resulted in a critical problem for modern society and future generations. Polyolefins, poly(ethylene terephthalate), Polyvinylchloride (PVC), polystyrene (PS), and high-impact polystyrene (HIPS) are among the most common components of plastic waste because they are among the most frequently used commercial plastics in our daily lives and in industry.Recycling mixed plastic residues in the form of blends is attractive from academic and industrial points of view because of the improvements in the impact strength , dimensional stability, stress cracking, and processability with respect to virgin blends[19 ]. In the present study, waste plastics are used as a filler for making bituminous roof mastic up to a level of 20 wt %. The viscoelasticity of a bitumen modified with waste 9wt% PE is analysed and compared to bitumen base. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  2 2. EXPERIMENTS PART Materials and preparation Waste plastics were collected from the garbage, sorted and shredded into coarse particles. The waste plastics and commercial bitumen were weighted and heated individually in an oven until melt. Molten waste plastic was poured into the molten bitumen and stirred vigorously to give a homogenous sample. The hot mixtures were then cast into a ring stamp with 25 mm diameter and 2 mm thickness for rheology testing . Measurements Solid-state dynamic viscoelastic measurements of all the pure bitumen and bitumen blends samples were accomplished in a Solid state institute, Research center Juelich, Germany. In this study we used an ARESrheometer (Advanced Rheology Expanded System, Rheometric Scientific Co.,) in the dynamic mode, under nitrogen atmosphere, plate-plate geometry with 25 mm in diameter to determine the rheological characteristics of the neat bitumen and bitumen blends. The measurements were performed over a wide range of temperatures ranged from 25°C to 160°C and frequencies from 100 to 0.1 radians per second. A sample ( about 1.0 g) was placed in the lower plate then the upper parallel plate was lowered for a tight contact with the sample. All the samples were held at a constant temperature of 50°C for 10 min, cooled to 25°C and measured at temperatures (25, 40, 60, 80, 100, 110, 120, 130°C, 145°C and 160°C). The applied strain were 2%. 3. RESULTS AND DISCUSSIONS In this section the results are presented in a master curves. The master curve is a single curve at which the experiments data which measured over a wide range of the temperature, T are shifted into this curve at a reference temperature T0 . By using of the timetemperature superposition principle which described by Williams-Landel-Ferry [20] as, log aT = -C1 (T-T0) /(C2+(T-T0)).Where aT is the horizontal shift factor and constants C1 and C2 are material specific. T0 is chosen in this study to be 25°C. aT shifts the data obtained at different temperatures along the log frequency,  axis as shown in Figure 1. Since aT shifts the high temperatures data toward the right -wing at low  and the low temperatures data toward the left -wing at high . In vertical direction the experiments data are shifted by bT (bT = 00 / TT  [21] ). Where  is the material density. bT shifts the data up-and-down by a factor related to the temperature. Where high temperatures data are multiplied by a factor and low temperatures data divided by a factor. Because the modulus decreases with increasing the temperatures. This master curve enable us to enlarge the range of the frequencies which it looks like data measured at a single temperature as a function of an extremely wide range of frequencies. As an example  can be enlarged from 102 -10-1 radians/s to 106 -10-6 radians/s and this range is difficult to measure by a machine until now. The master curves of the shear complex modulus, G* for bitumen and bitumen blends at 25°C are logarithmically plotted in Figure 2 against the angular frequency. This quantity of G* is a combination of the storage modulus (G') and loss modulus (G'') as, G*= G' + i G'' [38] .Where, G' is the ability of the material to store energy in the cycle of the deformation and G'' is the energy dissipated as heat in this cycle. Master curves of G* display two regions of behavior. These region are : the melt and rubber-like zones from the left side to the right side. The third regime of the dynamic glass transition is observed at very high frequency ( ~ 1109 ) in the case of pure bitumen as shown in Figure 2 because it could measured at low temperature (-10°C). At the flow regime, G* decreases further as shown in Figure 2. As the deformation shear rate increases, G* increases until the intermediate regime of a rubber-like plateau is observed. This rubber-like region is somewhat flat and it is nearly independent on the frequency as shown in Figure 2. Because this rubber like behavior reflects the elasticity at which the loss energy is minimum. But in the melt regime G* falls by many order of magnitude because of the high loss energy per the cycle of deformation due to the effect of the viscosity in this regime. The beginning of the melt regime is shifted toward low frequencies by the addition of waste PE to bitumen as shown in Figure 2. Since the melt regime begins at  ~ 2.4104and 30 radian/s in the cases of neat bitumen, bitumen9%PE , respectively. This because of the high elasticity due to the bitumen-PE network formation. The adding of waste plastics to bitumen showed a high effect as seen in Figure 2 the value of G* modulus for bitumen blend is higher than this of bitumen base.The difference in the values of G* between bitumen-PE and pure bitumen increases with decreasing the frequency. Where at  ~ 2.3105 radian/s the values of G* are 6.3106 and 1.4107 Pa for pure bitumen and bitumen-9% PE, respectively. At  ~ 2.3102 radian/s The values of G* in the case of bitumen-9%PE is higher than this of pure bitumen by 2 times. This factor reaches to 8 at  ~ 0.02 rad/s. This increase in G* modulus by the addition of waste PE reflects the interaction between polymer and bitumen which increases the stiffness. that leads to high stability for a long time of defromation (low frequencies) than neat bitumen. This interaction is mostly happened between polymer with saturate resins, owing to their closer solubility. Besides, Some authors have attributed this improvement to the existence of a third mixed phase modifying the asphaltene network. [22 ]. Since bitumen consists of matlenes and asphaltenes and the ratio of the asphaltenes to the maltenes has a significant effect on the viscoelastic properties of bitumen and, consequently, on its performance as road paving binders [23]. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  3 The master curves at 25°C of the storage (J') and loss compliance (J'') versus  are presented in Figures 3 and 4, respectively. J'() is a measure of the energy stored and recovered per deformation cycle, therefore is called the storage compliance. And J''() is a measure of the energy dissipated as heat per cycle of the sinusoidal deformation, for that is called the loss compliance. Figures 3-4 show the dynamic shear compliances moduli for bitumen blends compared to pure bitumen. These Figures show clearly two regions reflect the behavior of the material under the measured temperatures as a function of frequency as explained earlier in the case of G* () curves. As shown in Figures 3-4 the incorporation of the waste PE into bitumen affect on the J'() and J''() moduli. Since these moduli are enhanced for the bitumen blends. This is clear at  ~ 5.2103 radians/s (Fig.2) where the value of J' changed from 1.510 -7 for neat bitumen to 1.010 -7 Pa -1 in the case of bitumen/PE blend. But at low frequencies the effect is more noticeable. since at  ~ 5.910-2 radians/s, the values of J' become 4.010-5and 1.310-6 Pa-1 for pure bitumen, and bitumen blend, respectively. The same effect is observed also for J'' moduli in Figure 4. In this Figure at  ~ 91 radians/s the values of J'' are 4.310 -7 and 1.910 -8 Pa -1 for neat bitumen, bitumen-PE, respectively. This because of the matrix formation between the PE chains and bitumen which leads to increase the strength and stiffness. This increase in the stiffness and strength by the introduction of the waste PE to bitumen is confirmed also in the shear creep stress, J(t) in Figure 5. This Figure show J(t) as a function of time for pure bitumen and bitumen blends. As shown in Figure 5 J(t) increases with time and the difference between the values of J(t) in the case of neat bitumen and bitumen blends is higher at long times than at short times. Since at t ~ 200 seconds, the values of J(t) are, 1.110 -3 and 1.410 -5 Pa -1 for neat bitumen and bitumen-PE, respectively. This indicates the improvement of the stability of the bitumen for a long time by the addition of the waste PE due to network of bitumen-PE. Figure 6 presents log-log plot of the complex viscosity (*) as a function of  for neat bitumen and bitumen blends at 100°C. In this Figure * increases rapidly with decreasing  up to  = 0.001 radian/s after that it becomes independent on  . At this very low shear rates * is called the melt viscosity, 0 ( zero-shear viscosity). As shown in this Figure the incorporation of the waste plastics into the bitumen increases the viscosity over all the frequencies range. The difference between the viscosity of bitumen/PE blend and bitumen base is more noticeable at very low frequency (at 0). Since the values of 0 increase from 5.010 4 to 1.310 5 , 2.710 5 , 3.210 5 , 4.310 5 and 5.710 5 Pa.s by the addition of 3, 7, 9,13 and 20 % PET , respectively. This because the viscosity of the melt plastic is higher than this of bitumen and that is related to the length of the chains. The flow activation energy for neat bitumen and bitumen blends (bitumen-10%PET) are calculated from 0 by using the rheometric software and it is found to be 1.063 10 5 and 1.46 10 5 J/mol.K, respectively. The torque in NM as a function of frequency for neat bitumen and bitumen blends are logarithmically plotted at 100°C in Figure 7. The torque decreases with decreasing the shear rates as shown in Figure 7.This Figure evidences also that the addition of waste plastics to bitumen enhances the torque. Since the torque increases from 5.010 -4 to 1.310 -3 , 2.710 -2 , 3.210 -1 , 4.310 0 and 5.710 1 NM by the addition of 3, 7, 9,13 and 20 % PET , respectively. This because the formation of the bitumen-plastic matrix which leads to increase stiffness of the bitumen blends. 4. CONCLUSION Waste PE bags were used as a modifier in making improved bitumen. The blend compared to bitumen base was subjected to evaluate their response against temperature and frequency sweeps. By using an ARESRheometer (Rheometric Scientific, Co.) in the dynamic mode and parallel plate geometry with diameter 8 mm. The measurements were performed over a wide range of temperatures ranged from -10 to 60°C and frequencies from 100 to 0.1 radians per second. The flow activation energy for neat bitumen and bitumen blend are calculated from 0 by using the rheometric software and it is found to be 1.063 10 5 and 1.46 10 5 J/mol.K, respectively. It was found that, the complex modulus, shear compliance, torque and complex viscosity are enhanced by the incorporation of waste 9wt%PE. 5. ACKNOWLEDGMENTS The financial support by the International Bureau in Germany, helpful discussions of Dr. W.Pyckhout and Dr.S. Khale at FZJ, Germany are greatly acknowledged. REFERENCES 1. Y.Edwards, P.Redelius,Energy & Fuels, V17, P.511-520, 2003. 2. O. Gonzalez, J. J. Pena, M. E. Munoz, A. Santamaria, A. Perez-Lepe, F. Martinez-Boza, and C. Gallegos, V16, P. 1256 -1263, Energy Fuels, 2002. 3. Y.Khakimullin, A.Murafa, Z. Sungatova, E.Nagumanova, V.Khozin, V.36, P. 423-428, 2000. 4. A. Pérez-Lepe, F. J. Martínez-Boza, C. Gallegos, O. González, M. E. Muñoz and A. Santamaría, Fuel, V 82, P. 13391348, 2003. 5. P. R. Herrington, Y.Wu and M. C. Forbes, Fuel, V 78, P. 101-110 , 1999. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  4 6. A. Chaala, C.Roy and A. Ait-Kadi, Fuel, V 75, P. 1575-1583, 1996. 7. L.Champion-Lapalu, A.Wilson, G.Fuchs, D. Martin, J.-P. Planche, Energy & Fuels, V16, P.143-147, 2002. 8. A. H. Fawcett, T. McNally, Macromolecular Materials and Engineering, V286, P.126-137, 2001. 9. X. Lu and U. Isacsson, Fuel, V76, P. 1353-1359, 1997. 10. A. H. Fawcett, T. McNally, G. M. McNally, F. Andrews and J. Clarke, Polymer, V 40, P. 6337-6349, 1999. 11. Y. Ryabikin, V.Zashkvara , PETROLEUM CHEMISTRY,V43 P.286-288, 2003 12. A.Kishita, S. Takahashi, H.Kamimura, M.Miki, T.Moriya, H.Enomoto, JOURNAL OF THE JAPAN PETROLEUM INSTITUTE V46, P.215-221, 2003. 13. J.Jehlicka, O.Urban, J.Pokorny, SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY ,V59, P.2341-2352, 2003. 14. S.Rahmani, W.McCaffrey, J.Elliott, et al., IND ENG CHEM RES V42, P.4101-4108, 2003. 15. M.Rodriguez-Valverde, M.Cabrerizo-Vilchez, A. Paez-Duenas , et al., COLLOID SURFACE A, V222, P. 233-251, 2003 . 16. J.Brocks, R.Summons, R.Buick, et al., ORG GEOCHEM V34, P.1161-1175, 2003 17. 7. J.Bryan, K.Mirotchnik, A.Kantzas, J CAN PETROL TECHNOL V42, P. 29-34, 2003 18. A. H. Fawcett and T. McNally, Polymer, V 41, P. 5315-5326, 2000. 19. R.M. C. Santana, S. Manrich, Journal of Applied Polymer Science V88, P.2861-2867, 2003. 20. J.D. Ferry, "Viscoelastic Properties of Polymers", 3rd ed. ( Wiley, New York, 1980). 21. Mahmoud A.-Halim Abdel-Goad, PhD thesis, Muenster University, Germany, 2000. 22. A.Wilson, G.Fuchs, C.Scramoncin, D. Martin, J.P.Planche, Energy & Fuels, P.575-584, 2000. 23. F.Martinez-Boza, P. Partal, B.Conde, C.Gallegos, Energy & Fuels, V14, P. 131-137, 2000. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  5 Figure 1: Shifting the experiments data of G* for bitumen/PE measured at different temperatures into master curve at T0 =25°C by using aT and bT. Figure 2: Master curves of G* for bitumen/PE blend and bitumen base at T0 =25°C 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 3 10 4 10 5 10 6 10 7 b T a T Non-s h ifted exp.data Mas ter curve a t T 0 =25°C G * P a  ra d /s 1 0 -3 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 1 0 8 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 p ure b itum e n b it . -9 % P E G * P a  ra d /s International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  6 Figure 3: Master curves of J' for bitumen/PE blend and bitumen base at T0 =25°C Figure 4: Master curves of J'' for bitumen/PE blend and bitumen base at T0 =25°C 1 0 -4 1 0 -3 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 1 0 8 1 0 9 1 0 -7 1 0 -6 1 0 -5 1 0 -4 1 0 -3 ne a t b itum e n b it.-9 % P E J ' P a -1  ra d /s 10 -4 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 9 10 -9 10 -8 10 -7 10 -6 10 -5 10 -4 10 -3 p ure b itum e n b it . -9 % P E J " P a -1  ra d /s International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  7 Figure 5: The shear creep for bitumen/PE blend and bitumen base at T0 =25°C Figure 6: Master curves of * for bitumen/PE blend and bitumen base at T0 =25°C 10 -6 10 -5 10 -4 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 ne a t b itum e n b it . -9 % P E J t P a -1 t im e , s 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 ne a t b itum e n b it.-9 % P E  * P a .s  ra d /s International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 2, February - 2018, Pages: 6-13  8 Figure 7: Master curves of the torque for bitumen/PE blend and bitumen base at T0 =25°C 10 -4 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 9 10 -5 10 -4 10 -3 10 -2 ne a t b itum e n b it.-9 % P E to rq u e N M  ra d /s


Abstract: Chickpea is one of the main food crops in East Asia. As it contains high nutritional value, it has high demand in the world food market. Even though chickpea is mainly cultivated in India and China, Sri Lankan farmers did not trend to cultivate this crop. Therefore considerable amount of foreign exchange spent on import. This study will contribute to the country development in future.
          A study was conducted to study the feasibility of Chickpea cultivation in Ampara area. The research was done at Hardy ATI Farm, Ampara from 2nd December, 2015 to May, 2016. The land initially prepared and uniformly sized as 120 cm X 300 cm by having three replicates with the total of twelve beds which were used for testing plots. Three beds were used for establishing plants with (30 X 45) cm spacing recommended by the Department of Agriculture, India. Other 9 beds were planted with (25 x 40) cm, (35 X 50) cm, (35 X 40) cm. All the beds were provided with the same management practices such as seed planting, irrigation, weeding, pest & disease control and fertilizer applications. Germination time period (days), Germination percentage (%), plant heights (cm), Number of flowers were obtained for analysis. Complete Randomized Block Design (CRBD) was used with the Minitab database software.
          From the study it was identified that Chickpea plants performed significantly (p-0.05) well under Ampara climatic condition up to flowering stage when a spacing of (50 X 35) cm was used where germination percentage of 48.00±6.85 %, maximum plant height of 51.8 cm, highest no of flowers at 20th week with flower count of 29. Further this study could be repeated in alternative climatic regions for the best performances and profitability of Chickpea cultivation and to check yield analysis.

Philosophy

International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 1-4  1 Study on the Feasibility of Chickpea Cultivation in Ampara Area in Sri Lanka A.B.M. Jesfar 1 , A.L.M Rifky 2 , M.H.M Rinos 3 1 Department of Agriculture, Hardy Advanced Technological Institute, SLIATE, Ampara, Sri Lanka 2 Department of Bio System Technology, Eastern University, Sri Lanka, Chenkalady Sri Lanka 3 Department of Geography, South Eastern University of Sri Lanka, Oluvil. Sri Lanka Abstract: Chickpea is one of the main food crops in East Asia. As it contains high nutritional value, it has high demand in the world food market. Even though chickpea is mainly cultivated in India and China, Sri Lankan farmers did not trend to cultivate this crop. Therefore considerable amount of foreign exchange spent on import. This study will contribute to the country development in future. A study was conducted to study the feasibility of Chickpea cultivation in Ampara area. The research was done at Hardy ATI Farm, Ampara from 2 nd December, 2015 to May, 2016. The land initially prepared and uniformly sized as 120 cm X 300 cm by having three replicates with the total of twelve beds which were used for testing plots. Three beds were used for establishing plants with (30 X 45) cm spacing recommended by the Department of Agriculture, India. Other 9 beds were planted with (25 x 40) cm, (35 X 50) cm, (35 X 40) cm. All the beds were provided with the same management practices such as seed planting, irrigation, weeding, pest & disease control and fertilizer applications. Germination time period (days), Germination percentage (%), plant heights (cm), Number of flowers were obtained for analysis. Complete Randomized Block Design (CRBD) was used with the Minitab database software. From the study it was identified that Chickpea plants performed significantly (p-0.05) well under Ampara climatic condition up to flowering stage when a spacing of (50 X 35) cm was used where germination percentage of 48.00±6.85 %, maximum plant height of 51.8 cm, highest no of flowers at 20 th week with flower count of 29. Further this study could be repeated in alternative climatic regions for the best performances and profitability of Chickpea cultivation and to check yield analysis. Keywords: Chick Pea, Feasibility, Germination, Plant Height Corresponding authors ,  1. INTRODUCTION Background and Justification Chickpea (Cicer arietinum L.) is an important grain legume in Asia, and being a rich and cheap source of protein which can help people to improve the nutritional quality of their diet. It is mainly imported from India and other countries for usage. But Sri Lankan farmers do not trend to cultivate chick pea. Chickpea does best on fertile sandy, loamy soils with good internal drainage. Good drainage is necessary because even short periods of flooded or waterlogged fields reduce growth and increases susceptibility to root and stem rots. That shows the best soil conditions are available in Sri Lanka that mean it can grow successfully. Objectives 1. To find out the feasibility of Chickpea Cultivation in Ampara area. 2. To identify the suitable planting spaces and climatic conditions for Chickpea Cultivation in Sri Lanka 2. LITERATURE REVIEW Domesticated Chickpeas have been found in the aceramic levels of Jericho (PPNB) along with Cayony in Turkey and in Neolithic pottery at Hacilar, Turkey. They were found in the late Neolithic (about 3500 BCE) at Thessaly, Kastanas, Lerna and Dimini, Greece. In southern France Mesolithic layers in a cave at L'Abeurador, Aude have yielded wild Chickpeas carbon dated to 6790±90 BCE. By the Bronze Age, chickpeas were known in Italy and Greece. In classical Greece, they were called erebinthos and eaten as a staple, a dessert, or consumed raw when young. The Romans knew several varieties such as venus, ram, and Punic chickpeas. (Aguilera Y, 2009). Ancient people also associated chickpeas with Venus because they were said to offer medical uses such as increasing sperm and milk, provoking menstruation and urine and helping to treat kidney stones."White cicers" were thought to be especially strong and helpful. Chickpea is grown in tropical, sub-tropical and temperate regions. Kabuli type is grown in temperate regions while the desi type chickpea is grown in the semi-arid tropics. Chickpea is valued for its nutritive seeds with high protein content, 25.328.9 %, after dehulling. A small proportion of canned chickpea is also used in Turkey and Latin America, and to produce fermented food. Carter J (1999) Greater and more stable yields are the major goals of plant breeding programs. Chickpea yields usually average 400-600 kg/ha, but can surpass 2,000 kg/ha, and in experiments have International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 1-4  2 attained 5,200 kg/ha. Yields from irrigated crops are 20-28% higher than yields from rain fed crops. Hemalatha S, Platel K and Srinivasan K. (2007) In United States and Europe, chickpeas are marketed dried, canned, or in various vegetable mixtures. In Europe, mashed chickpeas from the Mediterranean are sold canned. The major chickpea growing countries are India, Pakistan, and Turkey in Asia, Ethiopia in Africa, California and Washington State in the U.S., Mexico and Australia. Yang Y, Zhou L, Gu Y, (2007). Further increases in yield could be attained from the use of germplasm wild relatives, for identification of new genes, and from new combinations of favorable genes already existing. Chickpeas mature in 3-7 months and the leaves turn brown/yellow during maturity. For dry seeds, the plants are harvested at maturity or slightly earlier by cutting them close to the ground or uprooting. The plants are stacked in the field for a few days to dry and later the crop is threshed by trampling or beating with wooden flails. Zia-Ul-Haq M, Iqbal S, Ahmad S (2008), Pittaway JK, Robertson IK and Ball MJ (2008). 3. MATERIAL AND METHODS Hardy Advanced Technological Institute (ATI) farm was selected to cultivate the chick pea because the soil condition and climatic condition are suitable for other cultivation practices therefore it was selected as our testing place. One deep plough and a harrowing were done by land preparation. Twelve beds were prepared for testing plots where 3 replicated were used to eliminate the error. Large soil particles, stone, sticks and unwanted material were removed from the beds and prepared with smooth surface for seedling. Locally available chickpea in the market, Chemical fertilizers such as Urea, TSP and MOP, Straw, Sprinkler irrigation system and hand tools were used for land preparation. Chemical and organic fertilizers were used as basal dressing. Three beds were used for establishing plants with (30 X 45) cm spacing recommended by the Department of Agriculture, India. Other 9 beds were planted with (25 x 40) cm, (35 X 50) cm, (35 X 40cm) respectively with 3 replicates. All the beds were provided with the same management practices such as seed planting, irrigation, weeding, pest & disease control and fertilizer applications. Germination time period (days), Germination percentage (%), plant heights (cm), Number of flowers were obtained for analysis. Complete Randomized Block Design (CRBD) was used with the Minitab database software. Large soil particles, stone, sticks and unwanted material were removed in the beds and prepared a smooth surface for seedling. Chickpea seed were soaked with adequate amount of water for 6 hours to stimulate the seed germination. Those seeds were planted in one 2.5 cm depth on Captan-treated bed. Three Chickpea seeds were planted in one hole. After seed planting, all the beds were covered by using straw to prevent external distortion. Germination of seeds was observed 5 to 6 days after seeding. Sprinkler irrigation system was used to irrigate Chickpea cultivation. The all beds were irrigated with two days interval. Straw mulch was not removed as it will help in soil moisture conservation. Weeding was done 14, 30 and 45 days after germination. No control measures were adopted since pest and disease problems were not observed in the Chickpea cultivation. There were no fertilizer recommendations in Sri Lanka as growing Chickpea is not common here. Therefore fertilizer recommendation used in groundnuts was used for this research. Fertilizer Urea (kg/ha) TSP (kg/ha) MOP (kg/ha) Basel Dressing 35 100 75 Top Dressing (at flowering) 30 4 . RESULT AND DISCUSSION Germination Percentage International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 1-4  3 Graph 01: Germination Percentage of each replicates in the plot. Germination percentage of the seeds were found to be 48.00±6.85 % in the replicates of the plot 3 (50 X 35) with the strong positive correlation (R3 = 0,949, P-Value = 0,000) while having the minimum percentage of 47.00 ± 6.67 % at plot 2 (40 X 25) with the strong positive correlation (R2 = 0,951, P-Value = 0,000). Plot 3 (50 X 35) showed a highest germination percentage which is acceptable because each holes in the prepared beds were added with 3 seeds each. Therefore, due to poor quality of seeds which was purchased at local retail shop, competition for the nutrients and other factors relevant to germinations were the limiting factor that controlled the germination process. Plant Height Plot 2 and 3 were having the plant height of 48.80 cm and 49.90 cm respectively. it revealed that the HATI farm is having the possibility to grow chick pea and can obtain a maximum plant height of 51.8 cm if suitable soil and climatic conditions are given. Graph 02: Plant height of each replicates in the plot. 1086420 50 40 30 20 10 0 days Y -D a ta R1 R2 R3 Total % Variable Germinated plants % Vs Days 000 010 020 030 040 050 060 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Plant Height Vs No of weeks PLOT 45 X 30 PLOT 40 X 25 PLOT 50 X 35 PLOT 40 X 35 No of week Plant Height (cm) International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 1-4  4 Number of Flowers Table 01: Weekly flower count of each replicates in the plot. Plots Spacing WEEKLY FLOWERING 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 45cm×30cm 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 6 9 19 23 24 40cm×25cm 0 0 0 0 0 0 0 0 0 0 0 0 0 1 2 8 12 20 23 23 50cm×35cm 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 10 14 26 28 29 40cm×35cm 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 7 11 22 27 28 Based on the result it revealed that Plot 3 (50 X 35) was having highest no of flowers at 20 th week with flower count of 29 and plot 1 showed the lowest no of flowers (24). It revealed that the HATI farm is having the possibility to grow chick pea and can obtain a maximum flower count of 29 if suitable soil and climatic conditions are given. 5. CONSTRAINTS The following problems were faced during the study period such as lack of good quality seeds were used as planting material, lack of books and cultivation manuals or guide lines to gain the basic knowledge on Chickpea cultivation, and the farm was not having permanent proper irrigation system. Even though the yield data could not be collected due to flower dropping due to prolonged drought condition and lack of irrigation water, the vegetative parameters such as germination time period, germination percentage, plant height and no of flowers showed better performances. According to the above results the Chickpea cultivation has a potential to be cultivated under the dry zone of Sri Lanka. No major pest and disease problems were observed during this cultivation period. 6. CONCLUSION The soil in Ampara area seems to be suitable for the growth of chick pea and comparatively plant growth and diseases were less in treatment 1, 2, 3 and 4. When comparing growth height of plant, it was observed that treatment 3 performed well compared to other treatments. Also under the flowering data, Spacing 3 is good than other treatments. REFERENCES [1] Aguilera Y, Esteban RM, Benítez V et al. Starch, functional properties, and microstructural characteristics in chickpea and lentil as affected by thermal processing. J Agric Food Chem. 2009 Nov 25;57(22):10682-8. 2009. [2] Carter J (1999) Chickpea Growers Guide: A Guide to the Production of Chickpeas (Agriculture Victoria Horsham), (ISBN 0 7311 4479 1). [3] Hemalatha S, Platel K and Srinivasan K. (2007) Influence of germination and fermentation on bioaccessibility of zinc and iron from food grains. European Journal of Clinical Nutrition. London: Mar 2007. Vol. 61, Iss. 3; p. 342-348. 2007. [4] Pittaway JK, Robertson IK and Ball MJ (2008), Chickpeas may influence fatty acid and fiber intake in an ad libitum diet, leading to small improvements in serum lipid profile and glycemic control. J Am Diet Assoc. 2008 Jun; 108(6):1009-13. 2008. [5] Yang Y, Zhou L, Gu Y, (2007) Dietary chickpeas reverse visceral adiposity, dyslipidaemia and insulin resistance in rats induced by a chronic high-fat diet. Br J Nutr. 2007 Oct;98(4):720-6. Epub 2007 Aug 1. 2007. [6] Zia-Ul-Haq M, Iqbal S, Ahmad S (2008) Antioxidant potential of desi chickpea varieties commonly consumed in Pakistan. Journal of Food Lipids, Volume 15, Issue 3, pages 326-342, August 2008. figures 3.


Abstract: Waste polyvinylchloride (PVC) pipes were reused in the modification of commercially available bitumen. Waste PVC/ bitumen blends were prepared by melt-mixing method. Rheological characteristics of the neat bitumen and bitumen blends samples were investigated. The rheological properties were determined using an ARES- Rheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from -10°C to 60°C and frequencies from 100 to 0.1 radians per second. Improvement in rheological properties.

Philosophy

International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  1 Reuse of Waste Plastic in the Modification of Rheological Characteristics of Bitumen Mahmoud Abdel-Halim Abdel-Goad and Hisham El-Shrief Chemical Engineering Dept., Faculty of Engineering, Minia University, Egypt (Correspondence to: Mahmoud Abdel-Goad: ) Abstract: Waste polyvinylchloride (PVC) pipes were reused in the modification of commercially available bitumen. Waste PVC/ bitumen blends were prepared by melt-mixing method. Rheological characteristics of the neat bitumen and bitumen blends samples were investigated. The rheological properties were determined using an ARESRheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from -10°C to 60°C and frequencies from 100 to 0.1 radians per second. Improvement in rheological properties. Keywords: bitumen; rheology; polymer modification, waste polyvinylchloride pipes. 1. INTRODUCTION Electricity the driving force of modern civilization, is indispensable in our day to day life. There are two basic types of electricity generation. One of which is through conventional energy resources which will get extinct in near future, hence demanding an alternative arrangement. Therefore, it is of great urgency to go for non-conventional energy resources. The non-conventional Bitumen is the black adhesive that binds flexible pavements on roads and airfields together. Bitumen is also used in other areas of application, such as waterproofing, flooring and joint materials. Almost all Bitumen originates from crude oil and is the residue of a refining process. It is well-known that bitumen is a very complex and temperature dependent material consisting of hydrocarbon molecules. Naphtenic-base crude oils often give a large yield of bitumen that may be of good quality, while paraffinic crude oils may give bitumen of good quality or yield bitumen not suitable for road construction [1]. Nowadays a very large majority of the roads are constructed using a mixture of bitumen (5 wt %) and mineral aggregates. Notwithstanding this low bitumen content, the performance of the road pavement depends to a large extent on the properties of bitumen itself, since it constitutes the only deformable component. The correlation between the complex colloidal structure of bitumen and its viscoelastic response is therefore a subject of scientific and technical interest [2 -7]. The addition of synthetic polymers to enhance service properties over a wide range of temperatures in road paving applications was considered a long time ago and nowadays has become a real alternative. As has been pointed out in the literature about bitumen and polymer/ bitumen blends[8 -17 ]. Polymer additives are well-known to improve the rheological properties of bitumen The polymer addition allows an increase in the resistance of the binder to permanent deformation at high temperature.Besides, the fracture properties including critical stress intensity factor at low temperature of polymer modified bitumen were shown to be higher than those of the bitumen base.To determine the crack propagation mechanism controlling fracture properties, previous studies have focused on establishing the relationship between the fracture properties and the morphology of polymer modified bitumen. [18] In recent years, the volume of municipal plastic waste has increased greatly, and this has resulted in a critical problem for modern society and future generations. Polyolefins, poly(ethylene terephthalate) (PET), Polyvinylchloride (PVC), polystyrene (PS), and high-impact polystyrene (HIPS) are among the most common components of plastic waste because they are among the most frequently used commercial plastics in our daily lives and in industry.Recycling mixed plastic residues in the form of blends is attractive from academic and industrial points of view because of the improvements in the impact strength , dimensional stability, stress cracking, and processability with respect to virgin blends[19]. In the present study, waste PVC pipes are used as a filler for making bituminous products for paving applications. The viscoelasticity of a bitumen modified with PVC wastes with level up to 11% is analysed and compared to neat bitumen. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  2 2. EXPERIMENTS PART 2.1 Materials and preparation Waste PVC pipes were collected from the garbage, sorted and shredded into coarse particles. The waste plastics and commercial bitumen were weighted and heated individually in an oven until melt. Molten waste plastic was poured into the molten bitumen and stirred vigorously to give a homogenous sample. The hot mixtures were then cast into a ring stamp with 25 mm diameter and 2 mm thickness for rheology testing . 2.2 Measurements Solid-state dynamic viscoelastic measurements of all the pure bitumen and bitumen blends samples were accomplished in a Solid state institute, Research center Juelich, Germany. In this study we used an ARESrheometer (Advanced Rheology Expanded System, Rheometric Scientific Co.,) in the dynamic mode, under nitrogen atmosphere, plate-plate geometry with 25 mm in diameter to determine the rheological characteristics of the neat bitumen and bitumen blends. The measurements were performed over a wide range of temperatures ranged from 25°C to 160°C and frequencies from 100 to 0.1 radians per second. A sample to be tested was placed in the lower plate then the upper parallel plate was lowered for a tight contact with the sample. All the samples were held at a constant temperature of 50°C for 10 min, cooled to 25°C and measured at temperatures in the range from -10 to 60°C. The applied strain was in the linear viscoelastic regime (2%). 3. RESULTS AND DISCUSSIONS In this section the results are presented in a master curves. The master curve is a single curve at which the experiments data which measured over a wide range of the temperature, T are shifted into this curve at a reference temperature T0 . By using of the timetemperature superposition principle which described by Williams-Landel-Ferry [20] as, log aT = -C1 (T-T0) /(C2+(T-T0)).Where aT is the horizontal shift factor and constants C1 and C2 are material specific. T0 is chosen in this study to be 25°C. aT is plotted as a function of temperatures in Figure 1. This Figure aT decreases with increasing the temperature by a slop about -0.18 up to about 25°C then decreases slowly until nearly becomes independent on the temperature. aT shifts the data obtained at different temperatures along the log frequency,  axis as shown in Figure 2. Since aT shifts the high temperatures data toward the left wing at low  and the low temperatures data toward the right -wing at high . In vertical direction the experiments data are shifted by bT (bT = 00/ TT  [21] ). Where  is the material density. bT shifts the data up-and-down by a factor related to the temperature as seen in Figure 2. Where high temperatures data are multiplied by a factor and low temperatures data divided by a factor. Because the modulus decreases with increasing the temperatures as shown in Figure 3, bT decreases with increasing the temperature. The master curve enable us to enlarge the range of the frequencies which it looks like data measured at a single temperature as a function of an extremely wide range of frequencies. As an example  can be enlarged from 102 -10-1 radians/s to 108 -10-4 radians/s and this range is difficult to measure by a machine until now. The master curves of the shear complex modulus, G* for bitumen and bitumen blends at 25°C are logarithmically plotted in Figure 4 against the angular frequency. This quantity of G* is a combination of the storage modulus (G') and loss modulus (G'') as, G*= G' + i G'' [22] .Where, G' is the ability of the material to store energy in the cycle of the deformation and G'' is the energy dissipated as heat in this cycle. Master curves of G* display two regions of behavior. These region are : the melt and rubber-like zones from the left side to the right side. The third regime of the dynamic glass transition is observed at very high frequency ( ~ 1109 ) in the case of pure bitumen as shown in Figure 4 because it could measured at low temperature (-10°C). At the flow regime, G* decreases further as shown in Figure 4. At very low frequencies ( ~ 0.0005) G* rises and that is more observable in the cases of neat bitumen and bitumen-11%PVC as shown in Figure 4. May be because of the traces of cross-linked reasons at the testing temperatures for a long time (very low frequencies). As the deformation shear rate increases, G* increases until the intermediate regime of a rubber-like plateau is observed. This rubber-like region is somewhat flat and it is nearly independent on the frequency as shown in Figure 4. Because this rubber like behavior reflects the elasticity at which the loss energy is minimum. But in the melt regime G* falls by many order of magnitude because of the high loss energy per the cycle of deformation due to the effect of the viscosity in this regime. The beginning of the melt regime is shifted toward low frequencies by the addition of waste PVC to bitumen as shown in Figure 4. Since the melt regime begins at  ~ 2.4104, 400, 100 and 30 radian/s in the cases of neat bitumen, bitumen-5%PVC, bitumen-7%PVC and bitumen-11%PVC, respectively. This because of the high elasticity due to the bitumenPVC network formation. The adding of waste plastics to bitumen showed a high effect as seen in Figure 4 the values of G* mouli for bitumen blends are higher than those of neat bitumen and G* is found to rise with increasing the waste PVC content as shown in Figure 5. The increase of G* at low frequency is higher than at high frequency . At  =100 radian/s (Fig.5a) G*~ (PVC)0.08 but at  =0.001 radian/s (Fig.5b) G*~ (PVC)0.15 as shown in Figure 5 . This increase in G* moduli by the addition of waste plastics reflects the interaction between polymer and bitumen which increases the stiffness. that leads to high stability for a long time of deformation (low frequencies) than neat bitumen. This interaction is mostly happened between polymer with saturate resins, owing International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  3 to their closer solubility. Besides, Some authors have attributed this improvement to the existence of a third mixed phase modifying the asphaltene network. [23 ]. Since bitumen consists of matlenes and asphaltenes and the ratio of the asphaltenes to the maltenes has a significant effect on the viscoelastic properties of bitumen and, consequently, on its performance as road paving binders [24]. 4. CONCLUSION Waste PVC pipes were used as a modifier in making improved bitumen for paving application. Various bitumen blends were prepared in the molten state by adding waste PVC up to 11%. The blends were subjected to evaluate their response against temperature and frequency sweeps. By using an ARESRheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from 10°C to 60°C and frequencies from 100 to 0.1 radians per second It was observed that improvement of rheological behavior of conventional bitumen compositions with the addition of PVC wastes. The PVC addition allows an increase in the resistance of the binder to permanent deformation. 5. ACKNOWLEDGMENTS The financial support by the International Bureau in Germany, helpful discussions of Dr. W.Pyckhout and Dr.S. Khale at FZJ, Germany are greatly acknowledged. REFERENCES 1. Y.Edwards, P.Redelius,Energy & Fuels, V17, P.511-520, 2003. 2. O. Gonzalez, J. J. Pena, M. E. Munoz, A. Santamaria, A. Perez-Lepe, F. Martinez-Boza, and C. Gallegos, V16, P. 1256 -1263, Energy Fuels, 2002. 3. Y.Khakimullin, A.Murafa, Z. Sungatova, E.Nagumanova, V.Khozin, V.36, P. 423-428, 2000. 4. A. Pérez-Lepe, F. J. Martínez-Boza, C. Gallegos, O. González, M. E. Muñoz and A. Santamaría, Fuel, V 82, P. 13391348, 2003. 5. P. R. Herrington, Y.Wu and M. C. Forbes, Fuel, V 78, P. 101-110 , 1999. 6. A. Chaala, C.Roy and A. Ait-Kadi, Fuel, V 75, P. 1575-1583, 1996. 7. L.Champion-Lapalu, A.Wilson, G.Fuchs, D. Martin, J.-P. Planche, Energy & Fuels, V16, P.143-147, 2002. 8. X. Lu and U. Isacsson, Fuel, V76, P. 1353-1359, 1997. 9. A. H. Fawcett, T. McNally, G. M. McNally, F. Andrews and J. Clarke, Polymer, V 40, P. 6337-6349, 1999. 10. Y. Ryabikin, V.Zashkvara , PETROLEUM CHEMISTRY,V43 P.286-288, 2003 11. A.Kishita, S. Takahashi, H.Kamimura, M.Miki, T.Moriya, H.Enomoto, JOURNAL OF THE JAPAN PETROLEUM INSTITUTE V46, P.215-221, 2003. 12. J.Jehlicka, O.Urban, J.Pokorny, SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY ,V59, P.2341-2352, 2003. 13. A. H. Fawcett and T. McNally, Polymer, V 41, P. 5315-5326, 2000. 14. S.Rahmani, W.McCaffrey, J.Elliott, et al., IND ENG CHEM RES V42, P.4101-4108, 2003. 15. M.Rodriguez-Valverde, M.Cabrerizo-Vilchez, A. Paez-Duenas , et al., COLLOID SURFACE A, V222, P. 233-251, 2003 . 16. J.Brocks, R.Summons, R.Buick, et al., ORG GEOCHEM V34, P.1161-1175, 2003 17. 7. J.Bryan, K.Mirotchnik, A.Kantzas, J CAN PETROL TECHNOL V42, P. 29-34, 2003 18. A. H. Fawcett, T. McNally, Macromolecular Materials and Engineering, V286, P.126-137, 2001. 19. R.M. C. Santana, S. Manrich, Journal of Applied Polymer Science V88, P.2861-2867, 2003. 20. J.D. Ferry, "Viscoelastic Properties of Polymers", 3rd ed. ( Wiley, New York, 1980). 21. Mahmoud A.-Halim Abdel-Goad, PhD thesis, Muenster University, Germany, 2000. 22. G.Heinrich, M.Klueppel, " Recent advances in the theory of filler networking in elastomers", Advances in Polymer Sciences, V160, P.1-44, Springer-Verlag Berlin Heidelberg, 2002. 23. A.Wilson, G.Fuchs, C.Scramoncin, D. Martin, J.P.Planche, Energy & Fuels, P.575-584, 2000. 24. F.Martinez-Boza, P. Partal, B.Conde, C.Gallegos, Energy & Fuels, V14, P. 131-137, 2000. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  4 Figure 1: aT of neat bitumen as a function of temperature Figure 2: shifting the experiments data of G* for neat bitumen at different temperatures to the reference temperature by using aT and bT . -10 0 10 20 30 40 50 60 10-2 10-1 100 101 102 103 104 105 106 107 a T Temp., °C 10-3 10-2 10-1 100 101 102 103 104 105 106 107 108 102 103 104 105 106 107 Master curve at 25°C 60°C 50°C 25°C 10°C -10°C bT aT aT non-shifted experiments data shifted data at T0=25°C G * P a  rad/s International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  5 Figure 3: bT of neat bitumen as a function of temperature Figure 4: Master curves of G* for bitumen and bitumen blends as a function of  at T0=25°C 10-410-310-210-1100101102103104105106107108 102 103 104 105 106 107 neat bitumen bit.-5% PVC bit.-7% PVC bit.-11% PVC G * P a  rad/s -10 0 10 20 30 40 50 60 0.1 1 b T Temp., °C International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2000-000X Vol. 2 Issue 12, December - 2018, Pages: 31-35  6 (a) Figure 5: The effect of the PVC content on G* of bitumen blends at a)  = 100 rad/s and b) =10-3 rad/s 0 2 4 6 8 10 12 106 107 =100 rad/s G * P a PVC wt% 0 2 4 6 8 10 12 103 104 =10 -3 rad/s G * P a PVC wt%


Waste polyvinylchloride (PVC) pipes were reused in the modification of commercially available bitumen. Waste PVC/ bitumen blends were prepared by melt-mixing method. Rheological characteristics of the neat bitumen and bitumen blends samples were investigated. The rheological properties were determined using an ARES- Rheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from -10°C to 60°C and frequencies from 100 to 0.1 radians per second. Improvement in rheological properties such as shear compliance, torque and complex viscosity were observed by the incorporation of the waste PVC into bitumen. The flow activation energy for neat bitumen and bitumen blends are calculated from the melt viscosity by using the rheometric software and it is found  to be 1.42 105, 1.5 105, 1.58 105 and 1.7 105 J/mol.K for neat bitumen, bitumen-5%PVC, bitumen-7%PVC and bitumen-11%PVC, respectively.

Philosophy

International Journal of Academic Engineering Research (IJAER) ISSN: 2000-001X Vol. 2 Issue 3, March - 2018, Pages: 12-15  12 Reuse of Waste Plastic in the modification of Rheological Characteristics of Bitumen: Part II Mahmoud Abdel-Halim Abdel-Goad Chemical Engineering Dept., Faculty of Engineering, Minia University, Egypt E-mail: Abstract: Waste polyvinylchloride (PVC) pipes were reused in the modification of commercially available bitumen. Waste PVC/ bitumen blends were prepared by melt-mixing method. Rheological characteristics of the neat bitumen and bitumen blends samples were investigated. The rheological properties were determined using an ARESRheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from -10°C to 60°C and frequencies from 100 to 0.1 radians per second. Improvement in rheological properties such as shear compliance, torque and complex viscosity were observed by the incorporation of the waste PVC into bitumen. The flow activation energy for neat bitumen and bitumen blends are calculated from the melt viscosity by using the rheometric software and it is found to be 1.42 105, 1.5 105, 1.58 105 and 1.7 105 J/mol.K for neat bitumen, bitumen5%PVC, bitumen-7%PVC and bitumen-11%PVC, respectively. Keywords: bitumen; rheology; polymer modification, waste polyvinylchloride pipes. 1. INTRODUCTION Bitumen is the black adhesive that binds flexible pavements on roads and airfields together. Bitumen is also used in other areas of application, such as waterproofing, flooring and joint materials. Almost all Bitumen originates from crude oil and is the residue of a refining process. It is well-known that bitumen is a very complex and temperature dependent material consisting of hydrocarbon molecules. Naphtenic-base crude oils often give a large yield of bitumen that may be of good quality, while paraffinic crude oils may give bitumen of good quality or yield bitumen not suitable for road construction [1]. Nowadays a very large majority of the roads are constructed using a mixture of bitumen (5 wt %) and mineral aggregates. Notwithstanding this low bitumen content, the performance of the road pavement depends to a large extent on the properties of bitumen itself, since it constitutes the only deformable component. The correlation between the complex colloidal structure of bitumen and its viscoelastic response is therefore a subject of scientific and technical interest [2 -7]. The addition of synthetic polymers to enhance service properties over a wide range of temperatures in road paving applications was considered a long time ago and nowadays has become a real alternative. As has been pointed out in the literature about bitumen and polymer/ bitumen blends[8 -17 ]. Polymer additives are well-known to improve the rheological properties of bitumen. The polymer addition allows an increase in the resistance of the binder to permanent deformation at high temperature. Besides, the fracture properties including critical stress intensity factor at low temperature of polymer modified bitumen were shown to be higher than those of the bitumen base. To determine the crack propagation mechanism controlling fracture properties, previous studies have focused on establishing the relationship between the fracture properties and the morphology of polymer modified bitumen[18]. In recent years, the volume of municipal plastic waste has increased greatly, and this has resulted in a critical problem for modern society and future generations. Polyolefins, poly(ethylene terephthalate) (PET), Polyvinylchloride (PVC), polystyrene (PS), and high-impact polystyrene (HIPS) are among the most common components of plastic waste because they are among the most frequently used commercial plastics in our daily lives and in industry. Recycling mixed plastic residues in the form of blends is attractive from academic and industrial points of view because of the improvements in the impact strength, dimensional stability, stress cracking, and processability with respect to virgin blends [19]. In the present study, waste PVC pipes are used as a filler for making bituminous products for paving applications. The viscoelasticity of a bitumen modified with PVC wastes with level up to 11% is analysed and compared to neat bitumen. 2. EXPERIMENTS PART Materials and preparation Waste PVC pipes were collected from the garbage, sorted and shredded into coarse particles. The waste plastics and commercial bitumen were weighted and heated individually in an oven until melt. Molten waste plastic was poured into the molten bitumen and stirred vigorously to give a homogenous sample. The hot mixtures were then cast into a ring stamp with 25 mm diameter and 2 mm thickness for rheology testing. International Journal of Academic Engineering Research (IJAER) ISSN: 2000-001X Vol. 2 Issue 3, March - 2018, Pages: 12-15  13 Measurements Solid-state dynamic viscoelastic measurements of all the pure bitumen and bitumen blends samples were accomplished in a Solid state institute, Research center Juelich, Germany. In this study we used an ARESrheometer (Advanced Rheology Expanded System, Rheometric Scientific Co.,) in the dynamic mode, under nitrogen atmosphere, plate-plate geometry with 25 mm in diameter to determine the rheological characteristics of the neat bitumen and bitumen blends. The measurements were performed over a wide range of temperatures ranged from 25°C to 160°C and frequencies from 100 to 0.1 radians per second. A sample to be tested was placed in the lower plate then the upper parallel plate was lowered for a tight contact with the sample. All the samples were held at a constant temperature of 50°C for 10 min, cooled to 25°C and measured at temperatures in the range from -10 to 60°C. The applied strain was in the linear viscoelastic regime (2%). 3. RESULTS AND DISCUSSIONS In this section the dynamic shear compliances moduli for bitumen blends compared to pure bitumen are plotted in Figures 1-2. Figure 1 presents the master curves at 25°C of the storage (J') as a function of frequency and loss compliance (J'') versus  are presented in Figure 2. J'() is a measure of the energy stored and recovered per deformation cycle, therefore is called the storage compliance. And J''() is a measure of the energy dissipated as heat per cycle of the sinusoidal deformation, for that is called the loss compliance. These Figures show clearly two regions reflect the behavior of the material under the measured temperatures as a function of frequency as explained earlier in the case of G* () curves. As shown in Figures 1-2 the incorporation of the waste PVC into bitumen affects on the J'() and J''() moduli. Since the shear compliance moduli are enhanced for the bitumen blends. This is clear at  ~ 5.2103 radians/s (Fig.6) where the values of J' changed from 1.510 -7 for neat bitumen to 1.010 -7 Pa -1 in the case of bitumen-11wt% PVC. But at low frequencies the effect is more noticeable and the difference in J' and J'' moduli among bitumen blends increases with PVC content. since at  ~ 5.910-2 radians/s, the values of J' become 4.010 -5 , 6.010 -6 , 2.310 -6 and 1.310 -6 Pa -1 for pure bitumen, bitumen-5wt%PVC bitumen7wt% PVC and bitumen-11wt% PVC, respectively. The same effect is observed also for J'' moduli in Figure 2. In this Figure at  ~ 91radians/s the values of J'' are 4.310-7, 1.110 -7 , 4.210 -8 and 1.910 -8 Pa -1 for neat bitumen, bitumen-5wt%PVC, bitumen-7wt% PVC and bitumen11wt% PVC, respectively. This because of the interaction between the PVC chains and bitumen, results in PVCbitumen network formation which leads to increase the strength and stiffness. This increase in the stiffness and strength by the introduction of the waste PVC to bitumen is confirmed also in the shear creep stress, J(t) in Figure 3. This Figure shows J(t) as a function of time for pure bitumen and bitumen blends. As shown in Figure 3 J(t) increases with time and the difference between the values of J(t) in the case of neat bitumen and bitumen blends is higher at long times than at short times and this difference increases with increasing the PVC content. Since at t ~ 200 seconds, the values of J(t) are, 1.110 -3 , 1.310 -4 , 4.110 -5 and 1.410 -5 Pa -1 for neat bitumen, bitumen-5wt%PVC, bitumen-7wt% PVC and bitumen-11wt% PVC, respectively. This indicates the improvement of the stability of the bitumen for a long time by the addition of the waste PVC due to network of bitumen-PVC. Figure 4 presents log-log plot of the complex viscosity (*) as a function of  for neat bitumen and bitumen blends at 25°C. In this Figure * increases rapidly with decreasing  up to  = 0.001 radian/s after that it becomes independent on  . At this very low shear rates * is called the melt viscosity, 0 (zero-shear viscosity). As shown in this Figure the incorporation of the waste PVC into the bitumen increases the viscosity over all the frequencies range. This increase in the viscosity is found to be rises with the increasing in the PVC content and it is more noticeable at very low frequency (at 0). The flow activation energy for neat bitumen and bitumen blends are calculated from 0 by using the rheometric software and it is found to be 1.42 10 5 , 1.5 10 5 , 1.58 10 5 and 1.7 10 5 J/mol.K for neat bitumen, bitumen-5%PVC, bitumen-7%PVC and bitumen11%PVC, respectively. Since the values of 0 increase from 1.510 5 to 8.910 5 , 2.910 6 and 8.510 6 Pa.s by the addition of 5, 7 and 11% PVC, respectively. This because the viscosity of the PVC-bitumen network is higher than this of bitumen. Besides, bitumen softens rapidly at low deformation rates. The torque in NM as a function of frequency for neat bitumen and bitumen blends are logarithmically plotted at 25°C in Figure 10. The torque decreases with decreasing the shear rates as shown in Figure 5. At very low frequencies ( ~ 0.0005) torque rises in particular in the cases of neat bitumen and bitumen-11%PVC as shown in Figure due to the traces of cross-linked reasons as explained above. This Figure evidences also that the addition of waste PVC to bitumen enhances the torque. Since the torque increases at  = 0.07 rad/s from 210 -4 to 110 -3 , 2.910 -3 , and 4.710 -3 NM by the addition of 5, 7 and 11%PVC to bitumen , respectively. This because the formation of the bitumenplastic matrix which leads to increase stiffness of the bitumen blends and the stiffness increases with increasing the waste PVC content. 4. CONCLUSION Waste PVC pipes were used as a modifier in bitumen for paving application. Various bitumen blends were prepared in the molten state by adding waste PVC up to 11%. The blends were subjected to evaluate their response against temperature and frequency sweeps. By using an ARESRheometer (Rheometric Scientific, Co.) under nitrogen atmosphere in International Journal of Academic Engineering Research (IJAER) ISSN: 2000-001X Vol. 2 Issue 3, March - 2018, Pages: 12-15  14 parallel plate geometry with diameter 25 mm. The measurements were performed over a wide range of temperatures ranged from -10°C to 60°C and frequencies from 100 to 0.1 radians per second The flow activation energy for neat bitumen and bitumen blends are calculated from 0 by using the rheometric software and it is found to be 1.42 10 5 , 1.5 10 5 , 1.58 10 5 and 1.7 10 5 J/mol.K for neat bitumen, bitumen-5%PVC, bitumen-7%PVC and bitumen-11%PVC, respectively. It was observed that improvement of rheological behavior of conventional bitumen compositions with the addition of PVC wastes. The PVC addition allows an increase in the resistance of the binder to permanent deformation. 5. ACKNOWLEDGMENTS The financial support by the International Bureau in Germany, helpful discussions of Dr. W.Pyckhout and Dr.S. Khale at FZJ, Germany are greatly acknowledged. REFERENCES 1. Y.Edwards, P.Redelius,Energy & Fuels, V17, P.511520, 2003. 2. O. Gonzalez, J. J. Pena, M. E. Munoz, A. Santamaria, A. Perez-Lepe, F. Martinez-Boza, and C. Gallegos, V16, P. 1256 -1263, Energy Fuels, 2002. 3. Y.Khakimullin, A.Murafa, Z. Sungatova, E.Nagumanova, V.Khozin, V.36, P. 423-428, 2000. 4. A. Pérez-Lepe, F. J. Martínez-Boza, C. Gallegos, O. González, M. E. Muñoz and A. Santamaría, Fuel, V 82, P. 1339-1348, 2003. 5. P. R. Herrington, Y.Wu and M. C. Forbes, Fuel, V 78, P. 101-110 , 1999. 6. A. Chaala, C.Roy and A. Ait-Kadi, Fuel, V 75, P. 15751583, 1996. 7. L.Champion-Lapalu, A.Wilson, G.Fuchs, D. Martin, J.P. Planche, Energy & Fuels, V16, P.143-147, 2002. 8. X. Lu and U. Isacsson, Fuel, V76, P. 1353-1359, 1997. 9. A. H. Fawcett, T. McNally, G. M. McNally, F. Andrews and J. Clarke, Polymer, V 40, P. 6337-6349, 1999. 10. Y. Ryabikin, V.Zashkvara , PETROLEUM CHEMISTRY,V43 P.286-288, 2003 11. A.Kishita, S. Takahashi, H.Kamimura, M.Miki, T.Moriya, H.Enomoto, JOURNAL OF THE JAPAN PETROLEUM INSTITUTE V46, P.215-221, 2003. 12. J.Jehlicka, O.Urban, J.Pokorny, SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY ,V59, P.23412352, 2003. 13. A. H. Fawcett and T. McNally, Polymer, V 41, P. 53155326, 2000. 14. S.Rahmani, W.McCaffrey, J.Elliott, et al., IND ENG CHEM RES V42, P.4101-4108, 2003. 15. M.Rodriguez-Valverde, M.Cabrerizo-Vilchez, A. PaezDuenas , et al., COLLOID SURFACE A, V222, P. 233251, 2003 . 16. J.Brocks, R.Summons, R.Buick, et al., ORG GEOCHEM V34, P.1161-1175, 2003 17. 7. J.Bryan, K.Mirotchnik, A.Kantzas, J CAN PETROL TECHNOL V42, P. 29-34, 2003 18. A. H. Fawcett, T. McNally, Macromolecular Materials and Engineering, V286, P.126-137, 2001. 19. R.M. C. Santana, S. Manrich, Journal of Applied Polymer Science V88, P.2861-2867, 2003. 20. J.D. Ferry, "Viscoelastic Properties of Polymers", 3rd ed. (Wiley, New York, 1980). 21. Mahmoud A.-Halim Abdel-Goad, PhD thesis, Muenster University, Germany, 2000. Figure 1: Master curves of J' for bitumen and bitumen blends as a function of  at T0=25°C Figure 2: Master curves of J' for bitumen and bitumen blends as a function of  at T0=25° 10 -4 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 -7 10 -6 10 -5 10 -4 10 -3 neat bitumen bit.-5% PV C bit.-7% PV C bit.-11% PV C J ' P a -1  rad/s 10 -4 10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 -9 10 -8 10 -7 10 -6 10 -5 10 -4 10 -3 10 -2 neat bitumen bit.-5% PV C bit.-7% PV C bit.-11% PV C J " P a -1  rad/s International Journal of Academic Engineering Research (IJAER) ISSN: 2000-001X Vol. 2 Issue 3, March - 2018, Pages: 12-15  15 Figure 3: Jt for bitumen and bitumen blends versus time at T0=25°C Figure 4: Master curves of * for bitumen and bitumen blends as a function of  at T0=25°C Figure 5: Master curves of torque for bitumen and bitumen blends as a function of  at T0=25°C 1 0 -8 1 0 -7 1 0 -6 1 0 -5 1 0 -4 1 0 -3 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 -9 1 0 -8 1 0 -7 1 0 -6 1 0 -5 1 0 -4 1 0 -3 1 0 -2 ne a t b i tum e n b i t.-5 % P V C b i t.-7 % P V C b i t.-1 1 % P V C J t P a -1 tim e , s 1 0 -5 1 0 -4 1 0 -3 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 1 0 8 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 n e a t b itu m e n b it.-5 % P VC b it.-7 % P VC b it.-1 1 % P VC  * P a .s  ra d /s 1 0 -4 1 0 -3 1 0 -2 1 0 -1 1 0 0 1 0 1 1 0 2 1 0 3 1 0 4 1 0 5 1 0 6 1 0 7 1 0 8 1 0 -6 1 0 -5 1 0 -4 1 0 -3 1 0 -2 1 0 -1 n e a t b itu m e n b it.-5 % P VC b it.-7 % P VC b it.-1 1 % P VC to rq u e N M  ra d /s


The dynamic viscoelastic properties of Polyvinylacetate with molecular weight 83000g/mol (PVA 83K ) were determined by using a Rheometer operated in the dynamic mode and 8 mm parallel plate over a wide range of temperature as a function of frequency. The measurements were performed successively in the parallel plate geometry using 8 mm plate instead of 25 mm. The creep compliance and viscosity are measured and evaluated. The melt viscosity,   is determined in this study for PVA 83K sample to be about 3.7* 107 Pa.s.

Philosophy

International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 9-11  9 Rheological Properties of Polyvinylacetate: Creep Compliance and Viscosity Mahmoud Abdel-Halim Abdel-Goad Chemical Engineering Dept., Faculty of Engineering, Minia University, Egypt E-mail: Abstract: The dynamic viscoelastic properties of Polyvinylacetate with molecular weight 83000g/mol (PVA 83K ) were determined by using a Rheometer operated in the dynamic mode and 8 mm parallel plate over a wide range of temperature as a function of frequency. The measurements were performed successively in the parallel plate geometry using 8 mm plate instead of 25 mm. The creep compliance and viscosity are measured and evaluated. The melt viscosity, 0  is determined in this study for PVA 83K sample to be about 3.7* 10 7 Pa.s. Keywords: Melt viscosity of Polyvinyacetate, biodegradable plastic 1. INTRODUCTION Rheology is concerned with the description of the mechanical properties of the various materials under the various deformation conditions. Polymer rheology is in its various aspects intimately entwined with molecular physics, continuum mechanics, and the processing of polymeric materials. At present, rheological investigations of polymers are processing at an enormously rapid rate, embracing a wide range of materials: biological objects, paste-like substances such as lubricants. The applied aspects of rheology are tied up with the development of new technological processes for the processing of plastics, elastomers and fibers [1]. The understanding of the relationship between the rheological properties of polymers and their molecular structure has considerably improved in the past few years with the interest of physicists in the matter and particularly with the development of molecular dynamics theories [2]. Besides, rheological measurements are used now as an analytical tool of polymer characterization [3]. In this work the rheological properties are investigated in details for a commercial PVA 83K. 2. EXPERIMENTAL SECTION Polydisperse PVA 83K sample was prepared for the Rheological measurements. In the disc form with 8 mm diameter and 1 mm thickness by using a press mould without vacuum at 50 C under 10 bar for 20 min. The preparation steps and conditions are summarized as follows: Approximately 0.1 g of the polymer is placed in a Teflon frame of dimensions 8 mm diameter and 1 mm thickness. This Teflon frame is introduced between two Teflon plates and positioned between two metallic plates in the mould. The sample is positioned on the lower plate followed by lowering the upper plate until just contact the upper Teflon plate. The sample is heated with heat rate 10 C/min. and pressed under 8-10 bar by lowering the upper piston for 20 min. The mould is cooled to 30  C , followed by taking the sample out. After preparation the sample for the measurement, the sample is placed on the lower plate of the ARES-Rheometer followed by lowering the stage until the sample just contacts the upper fixture completely. The ARES-Rheometer, consists of a test station, a furnace and liquid nitrogen controller. The test station contains the motor and transducer between which the sample to be tested is placed. The furnace is a forced convection enviromental chamber that encloses the sample. The gas temperature is controlled by two resistive heaters and the nitrogen gaseous is used during testing at or above room temperature. If test temperatures are below room temperature, liquid nitrogen is used. The temperature of the oven is maintained by a control loop that is closed around a platinum resistive thermometer. The normal force of the instrument should be kept around zero and the actual gap size is read electronically to be around 1 mm. The measuring program is adjusted to measure the sample over a wide range of temperature from 25  C up to 150  C as a function of frequencies in parallel plate geometry and dry nitrogen atmosphere .The strain was kept inside the linear regime in the whole frequency range. The strain is applied to the sample and the resulting stress is measured by the transducer. The stress signal generated by the sample separated into two components; an elastic part which is in the phase with strain and a viscouse contribution which is 90   out of phase with the strain. 3. RESULTS AND DISCUSSION The PVA83K sample was measured over a temperature range 25-150°C as a function of frequency. Different temperatures curves were shifted into single curve ( Master curve) to a reference temperature T0 (25  C)by means of the time-temperature superposition principle as proposed by Williams, Landel and Ferry (WLF) [8]. Figure 1 shows creep compliance (J(t). (J(t) is approximately equal to the stress relaxation modulus, G(t). G(t) is defined as the stress divided by strain at constant deformation and is plotted versus time. The boundaries of the plateau are temperature-dependent At short time the International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 9-11  10 corresponding region of the time scale is sometimes called glassy zone corresponds to the absence of any configurational rearrangements of the chain backbones It is clear from Figure 1 that at long time (J(t) falls rapidly. In terms of mechanical models, this corresponds to the complete relaxation of all springs in an array. The region of time scale in which (J(t) falls rapidly is often called the flow or terminal zone. If the viscoelastic (viscous and elastic at same time) behavior of the polymer is represented by a finite mechanical model, the decay of G(t) must at the end become exponential, proportional to e -t/τi where i  is the terminal relaxation time. Figure 2 shows the dynamic viscosity as function of the frequency . The dynamic viscosity is related to the loss modulus as, 0  =      G   0 lim [4]. At low frequency approaches the steady-flow viscosity, 0  . As shown in Figure 2 at very low frequency the viscosity begins to be independent ( 0  ) on the frequency. 0  is determined in this study for PVA 83K sample to be about 3.7* 10 7 Pa.s. This value depends on the temperature and molecular weight of the polymer. 4. CONCLUSION The rheological properties of PVA 83K are evaluated using an ARES Rheometer operated in the dynamic mode. The measurements were performed successively in 8 mm a parallel plate instead of 25 mm. The creep compliance and viscosity are measured and evaluated. The melt viscosity, 0  is determined in this study for PVA 83K sample to be about 3.7* 10 7 Pa.s. REFERENCES [1] Vinogradov, G.V.and Malkin, A.Ya, Rheology of Polymers (Mir Publishers, Moscow, 1980) [2] H. Nakatani, K.-H Nitta, and K. Soga, Polymer 40, 1547, 1999 [3] Billmeyer, Jr., F. W., Textbook of Polymer Science 3rd ed. ( Wiley, Singapore, 1984). [4] A.-Goad, A.-Halim, M., PhD thesis, Münster University, 2000. [5] Kuleznev, V.M.and Shershnev, V.A., The Chemistry and Physics of Polymers, (Mir Publishers, Moscow, 1990) [6] Ferry, J.D., Viscoelastic Properties of Polymers, 3rd ed. (Wiley, New York, 1980). [7] Eisele, U., Introduction to Polymer Physics, (Springer, Berlin, 1990). [8] Utracki, L.A., Polymer Alloys and Blends, Thermodynamics and Rheology (Hanser Publishers, Munich, 1990). [9] A.-Goad A.-Halim, M., Pyckhout,W., Allgiar, J., Fetters, L.J. and Richter, The Egyptian Society of Chemical Engineers, Vol.27, No. 2, P.245, Oct.2001. [10] Dara S.S., A text book of Engineering Chemistry, (S. Chand & Company LTD, Ram Nagar, New Delhi, 1999). [11] Fetters L. J., Lohse D.J., and Milner S.T., Macromolecules 32, No.20, 6847 (1999). [12] Baumgaertel M., Rosa M. E. De, Machado J., Masse M. and Winter H. H., Rheol. Acta. 31, 75 (1992). [13] J.K. Jackson, M.E. De Rosa, and H.H. Winter, Macromolecules 27, No. 9, 2426 (1994). International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 9-11  11 Figure 1: Master curve of the creep compliance for PVA 83K at T0 =25C. Figure 2: Plot of dynamic viscosity as a function of frequency for PVA 83K at T0 =25C. 10-5 10-4 10-3 10-2 10-1 100 101 102 103 104 105 10-8 10-7 10-6 10-5 10-4 10-3 J (t ) P a-1 time, sec. 10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 101 102 103 104 105 10-2 10-1 100 101 102 103 104 105 106 107 108 109  P a .s  rad/sec


Philosophy

International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 12-15  12 Rheological Properties of Polyvinylacetate: Storage-Loss Modulus and Relaxation Stress Mahmoud Abdel-Halim Abdel-Goad Chemical Engineering Dept., Faculty of Engineering, Minia University, Egypt E-mail: Abstract: The dynamic viscoelastic properties of Polyvinylacetate with molecular weight 83000g/mol (PVA 83K ) were determined by using a Rheometer operated in the dynamic mode and 8 mm parallel plate over a wide range of temperature as a function of frequency. The measurements were performed successively in the parallel plate geometry using 8 mm plate instead of 25 mm. The glass plateau regime is clearly observed because we could measure PVA 83K sample successively under its glass temperature. The storage and loss modulus and the relaxation stress are performed. Keywords: The storage and loss modulus of Polyvinyacetate, Relaxation stress. 1. INTRODUCTION Rheology is concerned with the description of the mechanical properties of the various materials under the various deformation conditions. Polymer rheology is in its various aspects intimately entwined with molecular physics, continuum mechanics, and the processing of polymeric materials. At present, rheological investigations of polymers are processing at an enormously rapid rate, embracing a wide range of materials: biological objects, paste-like substances such as lubricants. The applied aspects of rheology are tied up with the development of new technological processes for the processing of plastics, elastomers and fibers [1]. The understanding of the relationship between the rheological properties of polymers and their molecular structure has considerably improved in the past few years with the interest of physicists in the matter and particularly with the development of molecular dynamics theories [2]. Besides, rheological measurements are used now as an analytical tool of polymer characterization [3]. In this work the rheological properties are investigated in details for a commercial PVA 83K. 2. EXPERIMENTAL SECTION Polydisperse PVA 83K sample was prepared for the Rheological measurements. In the disc form with 8 mm diameter and 1 mm thickness by using a press mould without vacuum at 50 C under 10 bar for 20 min. The preparation steps and conditions are summarized as follows: Approximately 0.1 g of the polymer is placed in a Teflon frame of dimensions 8 mm diameter and 1 mm thickness. This Teflon frame is introduced between two Teflon plates and positioned between two metallic plates in the mould. The sample is positioned on the lower plate followed by lowering the upper plate until just contact the upper Teflon plate. The sample is heated with heat rate 10 C/min. and pressed under 8-10 bar by lowering the upper piston for 20 min. The mould is cooled to 30  C , followed by taking the sample out. After preparation the sample for the measurement, the sample is placed on the lower plate of the ARES-Rheometer followed by lowering the stage until the sample just contacts the upper fixture completely. The ARES-Rheometer, consists of a test station, a furnace and liquid nitrogen controller. The test station contains the motor and transducer between which the sample to be tested is placed. The furnace is a forced convection environmental chamber that encloses the sample. The gas temperature is controlled by two resistive heaters and the nitrogen gaseous is used during testing at or above room temperature. If test temperatures are below room temperature, liquid nitrogen is used. The temperature of the oven is maintained by a control loop that is closed around a platinum resistive thermometer. The normal force of the instrument should be kept around zero and the actual gap size is read electronically to be around 1 mm. The measuring program is adjusted to measure the sample over a wide range of temperature from 25  C up to 150  C as a function of frequencies in parallel plate geometry and dry nitrogen atmosphere .The strain was kept inside the linear regime in the whole frequency range. The strain is applied to the sample and the resulting stress is measured by the transducer. The stress signal generated by the sample separated into two components; an elastic part which is in the phase with strain and a viscouse contribution which is 90   out of phase with the strain. 3. RESULTS AND DISCUSSION The PVA83K sample was measured over a temperature range 25-150°C as a function of frequency. Different temperatures curves were shifted into single curve (Master curve) to a reference temperature T0 (25  C) by means of the time-temperature superposition principle as proposed by Williams, Landel and Ferry (WLF) [8]. International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 12-15  13 Figure 1 shows the master curves of storage, G    and loss modulus, G'' () for PVA 83K . In Figure 1 G'' () and G    are plotted against the radian frequency with logarithmic scales . The storage modulus, G    is the ability of the material to store energy and the loss modulus represents the losses in the energy per cycle of the deformation. On the dependencies of G', G'' (Fig. 1) on frequency we deal with the following characteristic points and regions. The most important for the loss modulus are the points of intersection of its frequency curve with the curve of frequency versus the storage modulus. In the region of relatively low frequencies the point of their intersection corresponds to the maximum of the loss modulus. On the frequency scale this point is conveniently taken as the beginning of the rubbery plateau. In this way the extent of the plateau is determined on the frequency scale. The point of the minimum of the loss modulus is important. In the region of the terminal zone ( which corresponds to the region of fluidity) the loss modulus is directly proportional to frequency. Figure 1 shows the glass plateau regime for PVA 83K at high frequency followed by the glass transition. The appearance of the glass regime because we could measure PVA 83K sample successively under its glass transition temperature with ARES rheometer. Since the glass transition temperature of PVA is 28 C [10] and the sample is measured at 25 C . The glass transition relates to the movement of the segments. The flatness of the rubber-like (plateau) regime is not clear due to the insufficient high molecular weight sample. As the result we cannot determine accurately the plateau modulus,  N G . Since the rubber-like regime is the indication of the entanglements where the chains are entangled each other above a certain molecular weight that called critical molecular weight, Mc. The attainment of the critical molecular weight is usually tied up to the appearance in the polymer of a spatial network of junctions of the type of molecular entanglements, which are characterized by weak intermolecular interaction and accordingly, by a low potential energy barrier. This accounts for the very slightly dependence of Mc on temperature. Mc equals to nearly two times [10] the entanglement molecular weight, Me which is the distance between the entanglement points can be determined as, Me = ρRT/  N G [11]. ρ is the density of the material, R is the universal gas constant and T is the reference temperature which is taken to be the room temperature in this study. And  N G is the plateau modulus that can be determined by different methods. From peak maximum in the loss modulus at the intersection point with the storage modulus as, max )06.060.4( GG N   [3].  N G could obtained also from the height of the plateau in Figure 1 at the point against to the minimum of loss modulus on the frequency scale. But these values of the plateau modulus are inaccurate because these points are not clear due to the insufficient high molecular weight (83000 g/mol) in addition to the large molecular weight distribution. The plateau regime is not clear also in the stress relaxation modulus (Fig.2) for the same reasons. The stress relaxation modulus, G(t) is defined as the stress divided by strain at constant deformation and is plotted versus time. The boundaries of the plateau are temperature-dependent At short time the corresponding region of the time scale is sometimes called glassy zone corresponds to the absence of any configurational rearrangements of the chain backbones It is clear from Figure 3 that at long time G(t) falls rapidly. In terms of mechanical models, this corresponds to the complete relaxation of all springs in an array. The region of time scale in which G(t) falls rapidly is often called the flow or terminal zone. 4. CONCLUSION The rheological properties of PVA 83K are evaluated using an ARES Rheometer operated in the dynamic mode. The measurements were performed successively in 8 mm a parallel plate instead of 25 mm. The glass plateau regime is clearly observed because we could measure PVA 83K sample successively under its glass transition temperature. The storage and loss modulus and the relaxation stress are performed. The accurate value of the plateau modulus  N G was difficult to obtain. Because of the insufficient high molecular weight and large molecular weight distribution. REFERENCES [1] Vinogradov, G.V.and Malkin, A.Ya, Rheology of Polymers (Mir Publishers, Moscow, 1980) [2] H. Nakatani, K.-H Nitta, and K. Soga, Polymer 40, 1547, 1999 [3] Billmeyer, Jr., F. W., Textbook of Polymer Science 3rd ed. ( Wiley, Singapore, 1984). [4] A.-Goad, A.-Halim, M., PhD thesis, Münster University, 2000. [5] Kuleznev, V.M.and Shershnev, V.A., The Chemistry and Physics of Polymers, (Mir Publishers, Moscow, 1990) [6] Ferry, J.D., Viscoelastic Properties of Polymers, 3rd ed. ( Wiley, New York, 1980). [7] Eisele, U., Introduction to Polymer Physics, (Springer, Berlin, 1990). [8] Utracki, L.A., Polymer Alloys and Blends, Thermodynamics and Rheology (Hanser Publishers, Munich, 1990). [9] A.-Goad A.-Halim, M., Pyckhout,W., Allgiar, J., Fetters, L.J. and Richter, The Egyptian Society of Chemical Engineers, Vol.27, No. 2, P.245, Oct.2001. International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 12-15  14 [10] Dara S.S., A text book of Engineering Chemistry, (S. Chand & Company LTD, Ram Nagar, New Delhi, 1999). [11] Fetters L. J., Lohse D.J., and Milner S.T., Macromolecules 32, No.20, 6847 (1999). [12] Baumgaertel M., Rosa M. E. De, Machado J., Masse M. and Winter H. H., Rheol. Acta. 31, 75 (1992). [13] J.K. Jackson, M.E. De Rosa, and H.H. Winter, Macromolecules 27, No. 9, 2426 (1994). The Abbreviations and notation: PVA 83K: Polyvinylacetate with molecular weight 83000g/mol.  : the angular frequency G' : the storage modulus G'' : the loss modulus i G : the relaxation strength G(t) : The relaxation stress T0 : The reference temperature  N G : the plateau modulus Figure 1: Master curve of storage and loss modulus as function of frequency for PVA 83K at T0 =25C. International Journal of Academic and Applied Research (IJAAR) ISSN: 2000-005X Vol. 2 Issue 3, March - 2018, Pages: 12-15  15 Figure 2: Master curve of the stress relaxation modulus for PVA 83K at T0 =25C. 10-4 10-3 10-2 10-1 100 101 102 103 104 105 106 102 103 104 105 106 G (t ), P a time, sec.


Philosophy

International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2643-640X Vol. 3 Issue 5, May - 2019, Pages: 8-10  8 Rheological Properties of Polyvinylacetate: Compliance and Relaxation Spectrum Mahmoud Abdel-Halim Abdel-Goad Petrochemicals Engineering Program, Faculty of Engineering, Minia University, Egypt (E-mail:) Abstract: The dynamic viscoelastic properties of Polyvinylacetate with molecular weight 83000g/mol (PVA 83K ) were determined by using a Rheometer operated in the dynamic mode and 8 mm parallel plate over a wide range of temperature as a function of frequency. The measurements were performed successively in the parallel plate geometry using 8 mm plate instead of 25 mm. The glass plateau regime is clearly observed because we could measure PVA 83K sample successively under its glass temperature. The rheological properties of polydisperse PVA 83K were completely studied. The storage and loss compliance and the relaxation spectrum are evaluated. Keywords: Viscoelastic properties of Polyvinyacetate, Relaxation spectrum, Compliance. 1. INTRODUCTION Rheology is concerned with the description of the mechanical properties of the various materials under the various deformation conditions. Polymer rheology is in its various aspects intimately entwined with molecular physics, continuum mechanics, and the processing of polymeric materials. At present, rheological investigations of polymers are processing at an enormously rapid rate, embracing a wide range of materials: biological objects, paste-like substances such as lubricants. The applied aspects of rheology are tied up with the development of new technological processes for the processing of plastics, elastomers and fibers [1]. The understanding of the relationship between the rheological properties of polymers and their molecular structure has considerably improved in the past few years with the interest of physicists in the matter and particularly with the development of molecular dynamics theories [2]. Besides, rheological measurements are used now as an analytical tool of polymer characterization [3-13]. In this work the rheological properties are investigated in details for a commercial PVA 83K. 2. EXPERIMENTAL SECTION Polydisperse PVA 83K sample was prepared for the Rheological measurements. In the disc form with 8 mm diameter and 1 mm thickness by using a press mould without vacuum at 50 C under 10 bar for 20 min. The preparation steps and conditions are summarized as follows: Approximately 0.1 g of the polymer is placed in a Teflon frame of dimensions 8 mm diameter and 1 mm thickness. This Teflon frame is introduced between two Teflon plates and positioned between two metallic plates in the mould. The sample is positioned on the lower plate followed by lowering the upper plate until just contact the upper Teflon plate. The sample is heated with heat rate 10 C/min. and pressed under 8-10 bar by lowering the upper piston for 20 min. The mould is cooled to 30  C , followed by taking the sample out. After preparation the sample for the measurement, the sample is placed on the lower plate of the ARES-Rheometer followed by lowering the stage until the sample just contacts the upper fixture completely. The ARES-Rheometer, consists of a test station, a furnace and liquid nitrogen controller. The test station contains the motor and transducer between which the sample to be tested is placed. The furnace is a forced convection enviromental chamber that encloses the sample. The gas temperature is controlled by two resistive heaters and the nitrogen gaseous is used during testing at or above room temperature. If test temperatures are below room temperature, liquid nitrogen is used. The temperature of the oven is maintained by a control loop that is closed around a platinum resistive thermometer. The normal force of the instrument should be kept around zero and the actual gap size is read electronically to be around 1 mm. The measuring program is adjusted to measure the sample over a wide range of temperature from 25  C up to 150  C as a function of frequencies in parallel plate geometry and dry nitrogen atmosphere .The strain was kept inside the linear regime in the whole frequency range. The strain is applied to the sample and the resulting stress is measured by the transducer. The stress signal generated by the sample separated into two components; an elastic part which is in the phase with strain and a viscouse contribution which is 90  out of phase with the strain. International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2643-640X Vol. 3 Issue 5, May - 2019, Pages: 8-10  9 3. RESULTS AND DISCUSSION The PVA83K sample was measured over a temperature range 25-150°C as a function of frequency. Different temperatures curves were shifted into single curve (Master curve) to a reference temperature T0 (25  C)by means of the time-temperature superposition principle as proposed by Williams, Landel and Ferry (WLF) [8]. Three regimes are found in Figure 1 where the storage, J'(w) and loss, J'' (w) compliance have roughly the appearance of mirror image of those of G' (w) and G'' (w). Since the rubber-like regime is the indication of the entanglements where the chains are entangled each other above a certain molecular weight that called critical molecular weight, Mc. A discrete relaxation spectrum using a small number of modes is derived to describe the relaxation behaviour of monodisperse polystyrene melts. Attention is focused on keeping the physical meaning of the relaxation times. Therefore, molecular dynamics theories are used in the terminal, plateau and transition zones and in the case of entangled melts. The spectrum is divided into three parts corresponding to three assumed different relaxation mechanisms: Rouse mechanism at short times, modified Rouse for tube equilibration and reptation with tube fluctuation in the long time range. This description only requires the knowledge of a limited number of parameters, namely the molecular weight of the polymer under investigation, the scaling law for Newtonian viscosity, the plateau modulus and the molecular weight between entanglements. The method is sucessfully applied to entangled monodisperse polystyrene melts and enables the recovery of final spectra containing only a few relaxation modes. If the viscoelastic (viscous and elastic at same time) behavior of the polymer is represented by a finite mechanical model, the decay of G(t) must at the end become exponential, proportional to e-t/τi where i  is the terminal relaxation time. The results of the extension in the number of elements in the Maxwell model without limit is a continuos spectrum that is called relaxation spectrum, H(T) (Fig. 2). The characteristic zones of the viscoelastic time scale are clearly apparent in H: the glassy zone to the left of the principle maximum, the transition zone where H drops steeply, the terminal zone where it approaches zero. 4. CONCLUSION The rheological properties of PVA 83K are evaluated using an ARES Rheometer operated in the dynamic mode. The measurements were performed successively in 8 mm a parallel plate instead of 25 mm. From the results obtaine, the viscoelastic properties of PVA could be studied with high accuracy. The storage and loss compliance and the relaxation spectrum are evaluated. 5. ACKNOWLEDGMENTS Support for this research was provided by International bureau in Germany. Rheological measurements were performed at research center Juelich, Germany.The helpful discussions of Dr.W.Pyckhout are grateful acknowledged. REFERENCES 1. Vinogradov, G.V.and Malkin, A.Ya, Rheology of Polymers (Mir Publishers, Moscow, 1980) 2. H. Nakatani, K.-H Nitta, and K. Soga, Polymer 40, 1547, 1999 3. Billmeyer, Jr., F. W., Textbook of Polymer Science 3rd ed. ( Wiley, Singapore, 1984). 4. A.-Goad, A.-Halim, M., PhD thesis, Münster University, 2000. Kuleznev, V.M.and Shershnev, V.A., The Chemistry and Physics of Polymers, (Mir Publishers, Moscow, 1990) 5. Ferry, J.D., Viscoelastic Properties of Polymers, 3rd ed. ( Wiley, New York, 1980). 6. Eisele, U., Introduction to Polymer Physics, (Springer, Berlin, 1990). 7. Utracki, L.A., Polymer Alloys and Blends, Thermodynamics and Rheology (Hanser Publishers, Munich, 1990). 8. A.-Goad A.-Halim, M., Pyckhout,W., Allgiar, J., Fetters, L.J. and Richter, The Egyptian Society of Chemical Engineers, Vol.27, No. 2, P.245, Oct.2001. 9. Dara S.S., A text book of Engineering Chemistry, (S. Chand & Company LTD, Ram Nagar, New Delhi, 1999). 10. Fetters L. J., Lohse D.J., and Milner S.T., Macromolecules 32, No.20, 6847 (1999). 11. Baumgaertel M., Rosa M. E. De, Machado J., Masse M. and Winter H. H., Rheol. Acta. 31, 75 (1992). 12. J.K. Jackson, M.E. De Rosa, and H.H. Winter, Macromolecules 27, No. 9, 2426 (1994). International Journal of Engineering and Information Systems (IJEAIS) ISSN: 2643-640X Vol. 3 Issue 5, May - 2019, Pages: 8-10  10 6. THE ABBREVIATIONS AND NOTATION: PVA 83K: Polyvinylacetate with molecular weight 83000g/mol.  : the angular frequency J' : the storage compliance J'' : the loss compliance J* : the complex compliance iG : the relaxation strength i : the relaxation time Figure 1: Master curve of the compliance for PVA 83K at T0 =25C. Figure 2: Plot of the relaxation spectrum for PVA 83K at T0 =25C. 10-5 10-4 10-3 10-2 10-1 100 101 102 103 104 105 106 107 101 102 103 104 105 106 H (  ) P a1 time, sec.