Degradation study of PVC and recycled PVC wastepipes in H2SO4 solution in diferent concentrations

Lima, F. A. S.; Nogueira, K. S.; Nogueira, A. S.; dos Anjos, T. P. D. June 26, 2012
Abstract The degradation behavior of blank and recycled PVC specimens obtained of wastepipes was investigated in diferente concentrations of H2 SO4 solution, whether 10, 20, 50 and 80 %. The specimens were attacked in the solution by diferente times whether 7, 14, 21 and 28 days. The mass loss, optical microscopy, infraded spectroscopy and x-ray diraction were used to characterize the specimens prior to and after attack. Results of the comparison showed that there was a non-linear mass loss for the specimens immersed in the solution. The micrographs showed that there was no correspondence between immersion time and the deterioration of surface...

Introduction

PVC is one of the most commonly used thermoplastic polymer. The demand for PVC exceeds 35 million tonnes per year. In recent years, the question of disposal of PVC waste has gained increasing importance in public discussion, resulting from the rapid growth of the PVC wastes [2].A suitable route, wich can recovery the energy and/or material content of these materials, whithout any special environmental problems, is recycling. Several scientists and industrialists suggested that PVC can be successfully recicled into a variety of products such as bottles, varios pipes, pipe ttings and other proles with good appearence and properties. They also claimed that the proles properties were unaected when the virgin PVC was replaced by PVC recyclates.There are many studies concerning with materials and chemical recycling of PVC.In this study, attention turns to the chemical resistance of the recicled PVC wastepipes.The infrastructure of macro sewage systems of huge cities has a big diversity of materials on pipes, ranging from the concrete into the PVC.The lack of deep studies on the characteristics of ideal materials to be applied on sewage systems turn materials science a impotant tool to devolp a disered class of materials that be resistante to the chemical reactions chains that occur in systems of collection and disposal of euent.

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2.1

Theoretical background
Corrosion and degradation of wastepipes

The formation of sulde acid in wastewater collection systems is given by the following sequence: 1 Sulphate-reducing bacteria require oxygen to burn o the organic matter in the wastewater.When the oxigen is not avaliable such microorganisms derive 2 avaliable on the aqueous midea leav the sulde ions from the sulfate ions SO4 2 S free; 2 The reaction of the sulde with water, results in sulde acid H2 S , known for its characteristic smell of rotten eggs; 3 The gas released is absorbed by the upper parts of the collector, again being oxidized and transformed into sulfuric acid H2 SO4 ; 4 The H2 SO4 attacks the tops of the collector.

2.2

Infra-red spectroscopy

The infra-red spectroscopy is a technique that provides informations about molecular structure, energy levels and chemical bonds based on the molecular vibrations.Spectroscopy studies the interaction of electromagnetic radiation with matter, considering the absorption of incident radiation by an atom and / or molecules. The infrared spectra are obtained by focusing radiation on the sample and determining the fraction of incident radiation absorbed [4]. During the molucular vibrational motion such variation may occur. When this oscillation is in resonance with the incident radiation, takes place, infrared absorption (or transmission) [3].The frequencies at which the molecules vibrate are called normal frequencies of vibration. The infrared active frequencies are the frequencies of normal vibrations associated with changes in the dipole moment of the molecule. Each maner the molecule could vibrate is so called normal mode of vibration. An infrared spectrum may be used to identify the species present in a sample by examination of its characteristic absorption bands associated with each molecule. The PVC infrared spectrum show a certain characteristic bands which can be seen in table . The bands are most important in the region of 600 700cm1 corresponding to the vibrational stretching C Cl. These bands are of complex origins and depend on the conformational structure of the polymer and the spatial position of the atoms near bonds C Cl. The other bands in the spectrum correspond to the dierent vibration C C and C H [1].

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3.1

Experimental
Chemical attack

The corrosion resistance of PVC and recycled-PVC was tested on specimens which were taken from PVC pipes, virgin and recicled respectively. The mass 2

Table 1: PVC infrared spectrum characteristic bands Wave number (cm1 ) Bands 2970 Stretch C H of CHCl 2912 Stretch C H of CH2 1435 and 1427 Deformation CH2 1331 and 1255 Deformation C H of CHCl 1099 Stretch C C 966 Rotation CH2 692, 637 and 616 Stretch C Cl Table 2: Specimens used in the attacks Recycled Specimens H2 SO4 Solution Concentration (%) R1 10 R2 10 R3 10 R4 10 R5 20 R6 20 R7 20 R8 20 R9 50 R10 50 R11 50 R12 50 R13 80 R14 80 R15 80 R16 80

Virgin Specimens V1 V2 V3 V4 V5 V6 V7 V8 V9 V10 V11 V12 V13 V14 V15 V16

Imersion Time (days) 7 7 7 7 14 14 14 14 21 21 21 21 28 28 28 28

of all the specimens were mesured, on an analytical balance accurate to four decimal places, before its were immersed in beakers containing, approximately, 60ml of H2 SO4 solutions in diferent concentrations, whether 10%, 20%, 50% and 80%. After that the specimens were removed every seven days, always removing a specimen blank and onother recycled of each four concentrations. Specimens were taken in four steps, hence the mass was mesured again after the attacks. The table 2 below ilustrate the specimens types wich been used in this study.

3.2

X-Ray diraction

X-ray diraction technique was used as a tool to indentify phases. The diraction was performed at the X-ray Diraction Laboratory of the Federal University of Cear a, on the Panalytical XPert Pro MPD device. The phases identication and, renement of measures were performed with PANalytical XPert HighScore Plus and DBWSTools 2.3, softwares respectively.

3.3

Infra-red spectroscopy

In this work the specimens were pulverized in an agate mortar to prepare the KBr pellet and thus perform the infrared spectroscopy. The powdered specimen is placed in the ring which is within the empastilhador, and then subjected to a pressure of 10 MPa in a hydraulic press. The Bruker spectrometer, model Vertex 70 was used.

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4.1

Results and discussion

Optical Microscopy

On the Fig. 1 is possible to observe the micrographs of, as received, PVC on the left and recycled PVC on the right. As is seen, the surface of the two samples shows no signs of degradation and they have the same appearance.

Figure 1: Micrographs of, as received, PVC on the left and recycled PVC on the right On Fig.2 is shown the micrographs os attacked PVC and Recycled PVC after seven days in 10% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 2: Micrographs of, as received, PVC on the left and recycled PVC on the right

On Fig.3 is shown the micrographs os attacked PVC and Recycled PVC after seven days in 20% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 3: Micrographs of, as received, PVC on the left and recycled PVC on the right On Fig.4 is shown the micrographs os attacked PVC and Recycled PVC after seven days in 50% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 4: Micrographs of, as received, PVC on the left and recycled PVC on the right

On Fig.5 is shown the micrographs os attacked PVC and Recycled PVC after seven days in 80% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 5: Micrographs of, as received, PVC on the left and recycled PVC on the right On Fig.6 is shown the micrographs os attacked PVC and Recycled PVC after fourteen days in 10% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 6: Micrographs of PVC on the left and recycled PVC on the right after 14 days attack in 10% concentrations H2 SO4 solution

On Fig.7 is shown the micrographs os attacked PVC and Recycled PVC after fourteen days in 20% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 7: Micrographs of PVC on the left and recycled PVC on the right after 14 days attack in 20% concentrations H2 SO4 solution On Fig.8 is shown the micrographs os attacked PVC and Recycled PVC after fourteen days in 50% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 8: Micrographs of PVC on the left and recycled PVC on the right after 14 days attack in 50% concentrations H2 SO4 solution

On Fig.9 is shown the micrographs os attacked PVC and Recycled PVC after fourteen days in 80% concentration of H2 SO4 . Now its possible to see the traces of degradation, this degradation can be conrmed by the mass loss of specimens.

Figure 9: Micrographs of PVC on the left and recycled PVC on the right after 14 days attack in 80% concentrations H2 SO4 solution

4.2 4.3

Infra-red spectroscopy X-ray diraction

X-ray diraction pattern for the two specimens analized shows only one phase, which is CaCO3 . The diratogram to PVC shows six difraction peaks whether (200),(020),(211),(-213),(220),(-222). While the diratogram to recycled PVC shows only ve peaks whether (200),(020),(-122),(220) e (-222). The diraction pattern to PVC and recycled PVC is shown in the Fig.

Figure 10: X-ray diraction pattern (a) virgin, (b) recycled.

4.4

Infra-red spectroscopy

Firstly was created a calibration curve with spectral data of PVC and recycled PVC, Fig. 11 (a) and (b) respectively.

Figure 11: Spectral data of PVC and recycled PVC: (a) virgin, (b) recycled.

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Conclusions Acknowledgements

References
[1] Beltr an M., Marcilia A., and Garcia J.C. Infrared spectral changes in pvc and plasticized pvc during galation and fusion. European Polymer Journal, 33:453456, 1997. [2] Mehdi Sadat-Shojai and Gholan-Reza Bakhshandeh. Recycling of pvc wastes. Polymer Degradation and Stability, 96:404415, 2011. [3] O. Sala. Fundamentos da espectroscopia Raman e no infravermelho. Editora da Universidade Estadual Paulista, 1996. [4] B. Stuart, B. George, and P. McIntyre. Modern infrared spsctroscopy. New York: CRC Press LLC, 1998.