Available online at www.sciencedirect.com
ScienceDirect Energy Procedia 50 (2014) 285 – 289
The International Conference on Technologies and Materials for Renewable Energy, Environment and Sustainability, TMREES14
Effect of Sunflower Oil on the Mechanical Permanence and The Thermal Properties Of Poly (Vinyl Chloride). Azeddine.ROUANEa (a)
(b)
,b
,Djamal ZERROUKIa, Mohamed.Tahar.BENANIBA b.
Laboratory Dynamics, Interactions and Reactivity Systems, university of Ouargla, 30000Ouargla, Algeria , Laboratory of Polymeric Materials Multiphasic, Faculty Of technology, University Ferhat ABBAS, Sétif 19000, Algeria. Email:
[email protected]
Abstract Hexyl phthalate Di-(-2-ethyl) (DEHP) is a conventional plasticizing for polyvinyl chloride (P VC) was partially replaced by organic plasticizer. Epoxidised sunflower oil (ESO) was epoxeded and characterized. The partial replacement of DEHP with epoxidized sunflower oil (ESO) and its mixtures have been analyzed, Testing of the hot air aging and mechanical testing of the dynamic stability of the color indicated ESO may be used as a secondary plasticizer , less volatile for PVC compared with the study of phthalate of Di (2-ethylhexyl) (DEHP) shows that the migration of DEHP may be substantially reduced without affecting the useful mechanical properties. An increase in the content of ESO has increased mechanical properties, while the composition with the oxirane oxygen hight ESO showed the best permanence propreties. © Ltd. This is an openbyaccess article under the CC BY-NC-ND license © 2014 2014Elsevier The Authors. Published Elsevier Ltd. (http://creativecommons.org/licenses/by-nc-nd/3.0/). Selection and peer-review under responsibility of the Euro-M editerranean Institute for Sustainable Development (EUM ISD). Selection and peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD)
Keywords:poly (vinyl chloride), plasticizer, DEHP, ESO, Tensile Test,Shore hardness
1. Introducti on: Poly(vinyl chloride), co mmonly abbreviated PVC is one of the most produced polymers on the world level. Its universality, its simplicity of implementation, its low cost still guarantees many applications in the everyday life [1]. The vegetable o il is subject to a gro wing interest in the context of increasing industrial applicat ions, d ue to the unique combination of the advantageous properties they exhib it (renewable resources, biodegradable and non -toxic). Among these, include sunflower oil. It has all these properties and gives with this type of materials a vast applicability in high technology. The sunflower oil was epoxid ised by a fast process, not pollutant. It used as thermal stabilizing for PVC and its performances proved completely interesting [2-3]. The aim of our work is to synthesize, characterize and study the behav ior of a "new" local plasticizer for polyvinyl chloride, sunflower oil epoxidized. As part of this work, blends (DEHP / DEHP) of co mpositions varying fro m 0 to 60% by weight have been made. Their thermal properties were studied by color scale SYNM ERO. The Formu lations processed on twin-ro ll mixer and an oven temperature 100 ° C for 7 days . * Corresponding author. Tel: +213 -0698567629. E-mail address:
[email protected]
1876-6102 © 2014 Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/). Selection and peer-review under responsibility of the Euro-Mediterranean Institute for Sustainable Development (EUMISD) doi:10.1016/j.egypro.2014.06.035
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Changes in physicochemical properties was fo llo wed by dynamic mechanical analysis (DMA) , and study by staining of the treated plates in the incubator and that of the two -cylinder mixer, as the study of mechanical properties, and the loss plasticizer in the oven and the solvent . 2-Preparation of the Sheets: The formu lations (poly meric + additive) are prepared at 170°C using a mixer apparatus type (RODOLFO COM ERIO, BUSTO.ARSIZIO) Co mposed of two cylinders. The Oxy ran index of epo xidised sunflower o il (ESO) is 5.4%. The co mposition of the formu lations containing PVC, stearate of Ca/Zn; DEHP with or without the presence of ESO for various compositions of ESO/DEHP is presented in the following table: Composition of the formulation (grams) Formulation
PVC
stearic Acid
Stearate of Ca/Zn
DEHP
ESO
00/60
100
1
1/1
60
00
05/55
100
1
1/1
55
05
10/50
100
1
1/1
50
10
15/45
100
1
1/1
45
15
20/40
100
1
1/1
40
20
25/35
100
1
1/1
35
25
30/30
100
1
1/1
30
30
40/20
100
1
1/1
20
40
50/10
100
1
1/1
10
50
60/00
100
1
1/1
00
60
3 . Results and Discussions 3.1. Mechanical properties 3.1 .1. Tensile Test The results presented in this part are obtained by calculation of the average of measurements on five tests reproductifs. The figures 3.1.1, 3.1.2 respectively represent the evolution of stress the rupture, the strain to failure and modulus of elasticity of the formulat ions based on PVC plasticized by the plasticizing system (ESO/DEHP). The addition of the ESO up to 15% in the plasticizer system maintains almost the same strain to failure. Beyond this concentration, the strain to failu re drops to a value of 2/3 when the concentration is 30%. St rain at failu re (İR) of the formulat ions plasticized by the system: epo xidised sunflower oil (ESO) and the dioctyl phthalate (DEHP) decrease proportionally with the incorporation of the ESO in the system. The modulus of elasticity of the plasticized formulat ions preserved almost constant up to 15%, and then it increases until the double for 30% of ESO in (ESO/DEHP) system.
Azeddine. Rouane et al. / Energy Procedia 50 (2014) 285 – 289
Stress to the rupture Vr (MPa)
12 10 8 6 4 2 0
60 OP 55 OP 50 OP 45 OP 40 OP 35 OP 30 OP 5 00- D 0 -D 10- D 15- D 20- D 25- D 30- D HTE HTE HTE HTE HTE HTE HTE
Fig.3.1.1. stress to failure evolution (ıR) of the formulations plasticized by (ESO/DEHP) system. 3.1 .2. Shore hardness Test A and D The Fig3.1.2 represents the evolution of Shore hardness A and D of the formu lations containing PVC plasticized with (ESO/ DEHP) System. It shows that the value of hardness A or D increases with the reduction in the rate of DEHP and with the increase in ESO in the plasticizing system. We can d ivide the plasticizing system into two parts. One with the rate of ESO lower or equal to 15%, the other fro m 15 to 30% . The performance of the ESO is very marked in the case or it used in the system with proportion ESO/ DEHP (15/ 45). More than the ESO exceeds the concentration of 15% and the DEHP decrease of 45%, the samples become rigid and breakable. 90 80
stress of the ruptur A stress of the ruptur D
70
Value
60 50 40 30 20 10 0
P 45 P 40 P 30 P 50 P 35 P 55 P 60 -DO 05 -DO 10 -DO 15 -DO20 -DO 25 -DO 30 -DO 0 0 E HT HTE HTE HTE HTE HTE HTE
Fig.3-1-2. Evolution of Shore hardness A and D of the formulations plasticized by system (ESO/DEHP). 3. 2. Spectroscopic Properties 3.2 .1. Characterization by Fourier transforms infrared spectroscopy (IRTF) In the case of a mixture of poly mer and addit ives, the fu ll infrared spectrum is considerably the addit ion of the spectra of the components. Any differences are due to the interactions between the components. The figure3.2.1 shows the superimposition of the FTIR spectra of 500 to 4000 cm-1 . The formu lat ions made into films depending on the plasticizer ESO / DEHP system. Table 3.2.1 co mbines the different bands detected in the formu lations considered and their functions in accordance with the preliminary characterization of the used products .
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Fig 3.2.1 infrared Spectra carried out with various formulations
Table .3. 2 .1 principal peaks present in the spectrum infrareds and their wavelengths. Wavelength (cm -1 ) 2950 1715 1470 1240 1120 1030 780
bending vibrations CH aliphatic asymmetrical stretching vibrational band C=O DEHP/ESO Aliphatic CH2 scissor for the methylene group Vibration of deformation of CH =CH 2 C=O of DEHP/ESO C-C C–Cl stretch
The presence of the absorption band of 2800-2950 cm -1 in all formu lations corresponds to the vibration of elongation of the aliphatic CH band. Also the band is observed at 1715 cm -1 which represents the vibration of elongation of the double band of C=O of plasticizers DEHP/ ESO. We note also the presence of the peak at 1470 cm -1 in the whole peaks of the formulat ions which represents the vibration of deformation Aliphatic CH2 scissor for the methylene group present in PVC (ESO/DEHP). mixture The peak at 1280 cm -1 represents the vibration of the CH band of - CH 2 which is present in all the formulat ions. The absorption band at 1150 and 1058 cm -1 characterizes the C-O-C band, which is present in mixture ESO/ DEHP; the peak intensity is relative to the rate of DEHP. Fro m the above figures we note the appearance of the same absorption spectra of the different formu lations . Th is is evident since for each formulat ion the same additives have been used. All spectra have the same allure. The difference is at the peak intensity is related to the proportion of the plasticizer ESO / DEHP system. the spectra intensity increase with inceaseing the amount of plasticizer . Conclusion: During the plasticizat ion of PVC by epoxidized sunflower oil as bioplastifiant, we studied different properties such as thermal, and we noted that as the ESO rate increases the degree of staining decreases, which means it is a good stabilizer .. The study of the mechanical properties showed that reduction in stress rupture, strain at failure and the Young modulus with the rise in the rate of ESO makes the mixture a little hard; this also seen in the study of Shore hardness A and D. The characterizat ion of the mixture by the test of migration (p lasticizer loss) Characterization of the mixture by the migrat ion test (loss of plasticizer) was seen that the amount of p lasticizer lost increases with the rate of ESO whatsoever for the aging in the oven or one that is in the solvent (methanol) so we found a high rate of ESO is not
Azeddine. Rouane et al. / Energy Procedia 50 (2014) 285 – 289
good because of the phenomenon of migration. [4] For the test of the mechanical dynamic analysis (DMA) we studied the difference in phase Tan į, E' (module of conservation) and E"(module of loss) Tg and also Domain of variation of Tg ( ǻT), we concluded that more the rate of ESO increases more Tg increases but ǻT (the variation of Tg) changes arbitraries , therefore a rate of high ESO makes lose some properties of the mixtures such as the facility with imp lementation, since Tg thus increased with a rate of high ESO it is bad plasticization. [5] References : [ 1 ] M.T . Benaniba, thermal Stabilization of vinyl polychloride of Algerian source, Memory of Magister, university Ferhat Abbas, Sétif, (1998) [2] G.Champetier, L. Monnerie, Introduction have macromolecular chemistry, Masson, Paris, (1969). [3] T . Saoseng, P. Chety, greasy substances, [ on line ]. Available on < http://membres.lycos.fr/tsaoseng/rapports/Corps_gras.htm > 2005. [4] V.limited liability company, Use of the sunflower oil like fuel, [ on line ]. Available on < http://valenergol.free.fr/dossiers/protection2001.htm >, (2001). [5] F. Chevassus, Phenomenon of decomposition and stabilization of the polymers (produced stabilization), French AFICEP-section SPE, (1977).
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