Waste Management 60 (2017) 100–111

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Composition analysis and characterization of waste polyvinyl chloride

(PVC) recovered from data cables
Sunil S. Suresh, Smita Mohanty, Sanjay K. Nayak ⇑
Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Plastics Engineering and Technology (CIPET), B-25, CNI Complex, Patia, Bhubaneswar,
Odisha 751024, India

a r t i c l e i n f o a b s t r a c t

Article history: Cables and wires are the indispensable parts of electronic equipments for transmission of both informa-
Received 6 June 2016 tion and electricity. Nowadays, data cables are widely used in the computer equipments for sending
Revised 26 August 2016 information and they become waste once its life cycle is completed. However, recycling of cables and
Accepted 27 August 2016
wires are mainly concentrating into the recovery of metals such as aluminium and copper, rather than
Available online 1 September 2016
other polymer present. Polymeric materials from the waste data cables are often disposed into landfills
or incinerated, since they have only lower value in recycling yard. From the data cables collected, it has
Keywords:
been estimated that the major constituents are copper (58.3%), polyvinyl chloride (19.9%) and polyethy-
WEEE
Data cable recycling
lene (16%). Similarly, polycarbonate (2.9%), silicon rubber (1.6%), steel (1.4%) and other material (0.4%)
Polyvinyl chloride such as cotton cord were also present as minor components. Out of these, polyvinyl chloride is the dom-
Degradation inant polymer present in data cables. Hence, the present work investigates the reprocessability of the
Plasticizers polyvinyl chloride recovered from the data cables and deals with issues such as premature degradation
during life cycle, assessment of plasticizers and degradation after reprocessing. Torque measurement
studies using torque rheometer revealed further mechanical recycling possibilites of the recovered poly-
vinyl chloride. Besides, the applicability of melt blending technique for processing recovered polyvinyl
chloride can be found out by analysing thermal behaviour by using thermogravimetric analysis, differen-
tial scanning calorimetry and heat distortion temperature.
Ó 2016 Published by Elsevier Ltd.

1. Introduction materials such as, conducting metals for transmission of informa-

tion and electricity like copper (Cu) and aluminium and different
The growth of technological advancement resulted in the devel- varieties of plastics as insulating and reinforcement material
opment of the Electrical and Electronic Equipment (EEE) products (Zabłocka-Malicka et al., 2015). Copper based data cables were
in modern society and increased consumption of computers, tele- one of the principle communication medium used for data trans-
visions, mobile phones and other IT equipments. The cables and missions in the IT sector, however, introduction of most efficient
wires are essential parts of all electronic gadgets for data and elec- and advanced fiber optical cable caused the replacement of Cu
tricity transmission from one source to another. The global market based data cables and thus increased the amount of Cu containing
of EEE continues to rise exponentially, meanwhile the life span of waste data cables (Unger and Gough, 2008).
the electronic gadgets becomes shorter. The worldwide enormous Considering the heterogeneous nature of scrap cables, they are
growth of EEE products resulted the generation of large volumes of usually grinded in mechanical grinder as whole and the metallic
Waste Electrical and Electronic Equipments (WEEE) (Buekens and parts were separated using electrostatic separator or dense med-
Yang, 2014; Sarath et al., 2015; Wath et al., 2011; Tanskanen, ium separation. The polymer waste after metal liberation is used
2013; Awasthi et al., 2016). for further recycling procedure (de Araújo et al., 2008; Sheih and
The majority of the cables and wires used in the EEE pose a Tsai, 2000; Zabłocka-Malicka et al., 2015).
number of problems for reuse and recycling due to its varying size Normally, the interest for the cable recycling mainly focused on
and heterogeneous nature. Cables and wires consists of variety to the recovery of the conductive metals, since it is predominant in
the cable waste (Lambert et al., 2015; Jadhao et al., 2016). Usually,
⇑ Corresponding author. polymeric outer layers after the isolation of metals have lower
E-mail addresses: [email protected] (S.S. Suresh), papers.journal@gmail. value in recycling and it is neglected (Zackrisson and Christina,
com (S.K. Nayak). 2014). They are incinerated either during isolation of the metals

http://dx.doi.org/10.1016/j.wasman.2016.08.033
0956-053X/Ó 2016 Published by Elsevier Ltd.
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 101

or after isolating the metals. Otherwise, they are discarded and material through different characterization methods. Several
finally end-up in landfills (Sadat-Shojai and Bakhshandeh, 2011). issues arise during the recycling of the PVC like the molecular dete-
However, the landfilling of polymer creates increased risk of chem- rioration during previous life cycle and different low molecular
ical leaching from them. weight plasticisers used for improving flexibility. FTIR has been
Polymer based materials are widely used for insulation of elec- used as the one of the suitable method for identifying premature
tronic cables because it exhibits combined properties like high degradation of PVC. The advance technique like GC–MS has been
flexibility, shockproof nature and easy processability. Currently widely used to study the plasticizer content in the PVC polymeric
different kinds of polymers such as polyvinyl chloride (PVC), poly- materials.
ethylene (PE), cross-linked polyethylene are being used for insula-
tion purposes (Lee et al., 2012; Zhao et al., 2013). PE and PVC are
2. Experimental
commonly utilized for the manufacturing of cables and wires used
in low voltage application (de Araújo et al., 2008).
2.1. Materials
Easy processing, inherent flame retardant nature and good insu-
lation behaviour of PVC makes it apt in the cable industry. In order
2.1.1. Sample collection
to improve the thermal stability, low modulus and brittleness of
The samples used for the study was collected from a certified E-
PVC, various additives were added into the polymer during its pro-
waste recycling plant, M/s E-Parisaraa, Bengaluru, India. The data
cessing. Flexible PVC is one of the commonly used thermoplastic as
cable products processed in the plant mainly comes from various
insulating material in cables and wires (Zabłocka-Malicka et al.,
sectors like household, governmental institutions and business
2015; Yang et al., 2007). The properties of the polymer depend
sectors from the different place of the country. The data cables
on the type and concentration of the plasticizers used. For improv-
were chosen because it is one of the major waste streams that
ing the flexibility of the cables different types of plasticizers were
come from IT equipments. For the further studies, a total of 178 dif-
added into the polymer. Low molecular weight phthalates are
ferent data cables were collected from the recycling plant which
the most generally used plasticizers in PVC (Cano et al., 2002;
were all non functional. Most of the data cables collected have
Linde and Gedde, 2014; Stringer et al., 2000).
length in between 70 and 100 m, and the weight of each cable
The main factor hindering the recycling of PVC is associated
ranges from 120 to 200 g.
with ageing of material during its life cycle. Since most of the data
cables are used in contact with environment, the presence of oxy-
gen, humidity, UV radiation, temperature and electric field has also 2.1.2. Sample preparation
been shown to induce changes in the chemical structure of PVC. The data cables were disassembled, as shown in Fig. 1, manually
The exposure of PVC in nature initiates changes in the mechanical with hand cutter and wire stripping tool so as to isolate plastic por-
properties, even for a short exposure period has also been reported tions like outer plastic layer (outer jacket), supporting cable,
to decrease in the percentage of elongation (Merah et al., 2013; Shi twisted wire and metals like copper and steel. Outer jacket plastic
et al., 2008; Brebu et al., 2000). layer and twisted wire are peeled off from data cable and remain-
The main aim of this work is to sort out PVC from the data ing metals and other parts were kept aside for further studies.
cables to study the reprocessability of the material using melt Materials were separated by visual identification into three frac-
blending technique. Composition of the data cables were studied tions like plastics, metals and others. The obtained plastic material
by the Fourier transform infrared-attenuated total reflectance were cut into small pieces, washed well with mild detergent solu-
spectroscopy. PVC was chosen for further recycling studies since tion and subsequently with de-ionised water to remove dirt,
it is a major polymer component in data cables as well as it enables attached grease and oily materials. Thereafter whole material
easy recovery from data cables. The studies were extended to find was kept in the oven for 5 h at 60 °C prior to weighing, for making
out the reprocessability or recycling ability of the PVC insulation it dry/moisture free.

Fig. 1. Disassembly procedure adapted in current study for data cables.

102 S.S. Suresh et al. / Waste Management 60 (2017) 100–111

The plastic materials in the data cables were identified by resin solvent added and the process repeated. The solvent fractions
identification code (RIC) and FTIR spectra of randomly selected obtained were combined together and concentrated using rotary
polymers. The colour of the polymeric material was also identified evaporator. The concentrated solvent fraction was used for identi-
along with the type of the polymer. fication of plasticizers with the help of GC/MS.

2.2. Methods 2.2.2. Torque rheometer analysis

The torque analysis was carried out in Haake rheocord 9000
2.2.1. Physiochemical analysis using a Rheomix 600 mixing chamber of 69 cm3 with roller style
2.2.1.1. Fourier transform infrared spectroscopy-attenuated total mixing blades. The rotor speed was optimized to 50 rpm, with mix-
reflectance (FTIR-ATR). FTIR spectra of the different polymers in ing time of 5 min for processing the material to prevent further
the data cables were recorded in order to identify the characteristic degradation in mixing chamber. The polymer was processed at
polymers present in the data cables. Each polymer present in the 165 °C. As the free volume of the mixing chamber was 70% of the
data cables was identified based on evaluation of the molecular total volume, 60 g of total weight was taken for the reprocessing
vibrations from the various functional groups in it. The recovered study, which was calculated on the basis of PVC density.
polymer samples from data cable were washed with detergent
solution and de-ionised water to remove the dust and all other
2.2.3. Mechanical analysis
attached objects. The polymer samples were dried well with vac-
A 10 kN M/s Instron, UK (model 3382) mechanical testing sys-
uum oven prior to FTIR-ATR analysis. Subsequently, FTIR-ATR tech-
tem with a grip separation speed of 10 mm/min was used for ten-
nique is also used for estimation of the degradation level of
sile testing. The samples for the tensile analysis were prepared via
polymeric materials during its service period.
twin-screw compounder M/s DSM 15 ml xplore, Netherland. The
The carbonyl and polyene group vibrations present in the r-PVC
temperature profile was set to 165 °C, 170 °C and 170 °C for the
were analysed using FTIR-ATR in order to calculate carbonyl and
three consecutive zones with a screw speed of 55 rpm. The extru-
polyene indices value. The r-PVC was extracted with tetrahydrofu-
date was collected and moulded to dumbbell shaped specimens,
ran (THF) before analysing carbonyl and polyene group vibrations,
having dimension of 165  12.7  3 mm, in a mini injection jet at
to remove the all plasticizers from r-PVC, since their spectra can
a mould temperature of 40 °C and melt temperature of 160 °C with
interfere with the degradation peaks formed by the PVC.
140-psi pressure. Tensile test method was carried out according to
ASTM D-638 specification, at room temperature. Average values of
2.2.1.2. Extraction procedure for removal of plasticizers. The polymer
the five specimens were represented as result.
dissolution technique was used for extraction of plasticizers from
r-PVC. The r-PVC was accurately weighed into 250 ml glass jar
and dissolved in 100 ml of THF. The glass jar was closed with a 2.2.4. Thermal analysis
lid and ultra sonicated for 2 h at room temperature. The ultra son- Thermal transitions of the waste plastic materials were studied
ication ensures the proper contact between the polymer sample using differential scanning calorimetry (DSC) instrument, DSC Q20,
and solvent. 75 ml ethanol was added as an antisolvent to repre- TA instruments USA. 5–7 mg samples were subjected to first heat-
cipitate r-PVC from the resulting mixture, and the solvent fraction ing from room temperature to 180 °C, held for 5 min to remove the
was filtered off. The reprecipitated r-PVC was further washed well previous thermal history, followed by a slow cooling to 30 °C at a
with methanol solution. The residue obtained was dried and sub- rate 10 °C/min, and reheated again (30–300 °C) until the degrada-
jected to FTIR-ATR analysis for carbonyl and polyene molecular tion, under nitrogen atmosphere.
vibration. Thermal stability of waste plastics was evaluated by using ther-
All the samples were examined directly with M/s Nicolet 6700, mogravimetric analyser instrument, TGA, Q50, TA instrument USA.
Thermoscientific, USA FTIR-ATR spectrometer without any further About 7 mg of sample was heated from 50 to 700 °C at a rate of
modification of samples. All the analysis was done in the range of 10 °C/min under nitrogen flow and corresponding change in
4000–400 cm
1 with the scan rate of 4 cm
1/s using attenuated weight vis a vis temperature was noted.
total reflectance attachment. Heat distortion temperature (HDT) measurement were carried
out following ASTDM D 648 at a heating rate of 2 °C/min using
2.2.1.3. Density analysis. Density measurement of recovered plastic Gotech testing machine, Taiwan.
material from data cables were studied according to the ASTM
D792 method. A set of 25 replicate predried samples of each poly- 3. Results and discussion
mers in the data cable was prepared and density was calculated.
The average value is taken as density. Further, the obtained value 3.1. Structural and composition analysis of data cable
was compared with virgin polymer since the density of the speci-
men depends on previous thermal history, loss of plasticizer, com- Fig. 2(a) represents the disassembled sample of a data cable and
position and porosity of the material (ASTM, 1991). schematic cross-sectional representation of the data cable is given
in Fig. 2(b). The outer layer of data cable is mainly composed of
2.2.1.4. Gas chromatograph/mass spectrometer for analysis of plasti- PVC, which provide the protection to the internal wires from the
cizer. Qualitative analysis of the plasticizer in r-PVC was performed outer environment and act as electrical shock proof to the users.
on the GC–MS chromatograph (GC: Agilent 7890A coupled with Twisted pair copper wire in data cables were mainly used for data
MS: 5975C MSD) by comparing the retention times and the spec- transfer, which is made up of copper core with a plastic insulation
tral characteristics with the corresponding particular peaks in the (www.data-cabling-expert.tv, 2015). FTIR studies reveal the use of
NIST 2011 reference library search. PE in twisted pair cable for insulation from external factors. Pri-
Samples for GC–MS analysis were prepared by dissolving accu- mary colours and its combination are given to the PE insulation
rately weighed 1 g of grated r-PVC in a glass bottle with 100 ml of for identification purposes. However, difficulties in peeling PE
hexane, followed by the ultra sonication for 2 h. The extraction material from the Cu metal hinder the further recycling of twisted
procedure was carried out in room temperature. The ultra sonica- pair wires. In most of the data cables, a long cord of PE running par-
tion can ensure the complete leaching of plasticizers from the poly- allel to the twisted pair wire act as support and prevents misplac-
mer. The solvent fraction was decanted after each 2 h and fresh ing of the individual wires from the proper positions.
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 103

Fig. 2. (a) Disassembled data cable. (b) Schematic cross section image of data cable.

Fig. 3 represents the major findings about the data cable com- 3.2. Analysis of polymers in data cables using FTIR
position from the total collected waste. Metals are the predomi-
nant fractions of the data cables which hold 59.7 wt%. A major FTIR spectroscopy is a good analytical tool for structural
portion of the sample carries copper metal, as it is a metallic con- analysis of recycled materials. The components of the data
ductor used for the data transmission. Copper used in the data cables were examined by FTIR spectroscopy. FTIR measurements
cables alone carries 58.3 wt% of the total data cable waste used show characteristic spectra for PVC outer layer (Fig. 4(a)) and
for study. FTIR studies convey that data cable mainly consists of peaks obtained were matching with the previous reports
the thermoplastics like PVC, PE, polycarbonate (PC) and silicon rub- (Gawade et al., 2007; Zhang et al., 2013; Soman and Kelkar,
ber. PVC & PE are widely used in the data cable for the insulation of 2009; Krimm et al., 1963). The characteristic peak at
the metallic portion and PC is used in the connector segment for 2957 cm
1 represent out of phase stretching of CAH in the
holding metallic connector. Silicon rubber bush act as a support neighbouring CHACl group and 2916 cm
1, 2850 cm
1 vibration
and vibration absorber in between connector and cable because region represents stretching of CAH in CH2 and in phase
of its low modulus. Similarly, materials like cotton cords were used stretching of CH2 respectively. Furthermore, a strong band at
in some of the data cables instead of supporting cable. Only 29 wt% 1425 cm
1 is because of in phase bending of CH2. The CACl
of the waste data cable plastics comprise of RIC code with regard to stretching and bending vibration frequencies lie below the
the type of the polymer used and in all other samples either not 706 cm
1. The absorbance band at 609 and 640 cm
1 represents
properly mentioned or wiped out during its service period. The col- stretching vibrations of CACl bonds. However, some of the
our of the data cable varies and depends on the type of usage and absorbance peaks in PVC cannot be studied with FTIR because
manufacturer, although almost 58 wt% of collected data cable were of the overlapping with other vibrations due to the presence
black in colour. Data cable consist of 41.3% of polymers in which of additives.
PVC is the largest fraction followed by PE, PC and silicon rubber FTIR spectra of twisted wire insulation and supporting cord
found as a minor portion in this study. However, the manual recov- were given in Fig. 4(b) and (c) respectively. FTIR analysis indi-
ering of PE is considerably difficult since it is attached to metallic cates spectra of twisted wire and supporting cords and is analo-
copper wire. gous to PE spectra. The strong sharp peaks at 2914 (2915 in
supporting cable) & 2847 cm
1 is attributed to the asymmetric
and symmetric stretching vibrations of CH2 groups in the PE
polymer chains respectively. A sharp band at 1468 cm
1 repre-
sents the bending deformation of methylene in PE polymer
chain. The absorbance band at 1377 cm
1, 718 cm
1 corresponds
to the symmetric deformation of CH3 and CH2 rocking deforma-
tion respectively. However, twisted wire insulation polymeric
material shows a broad band at 3100–3500 cm
1 and a weak
band at 1737 cm
1 due to the presence of hydroxyl and carbonyl
group vibrations respectively. Since the twisted wire polymeric
portion are covering the conductive metal part, the lower voltage
produced in the conductor perhaps catalysis the degradation and
results a change in chemical structure. However, the characteris-
tics molecular vibrations of hydroxyl and carbonyl group are
absent in the supporting cable and can be related to the absence
of degradation.
FTIR spectra of connectors used in the data cable bring out
the fact that the polymeric material is mainly composed of
polycarbonate (Fig. 4(d)). An intense triplet peak in the range
of 1265–1030 cm
1 were considered as the major identification
Fig. 3. Data cable composition after dismantling analysis. peak of polycarbonate resulted from the vibration modes
104 S.S. Suresh et al. / Waste Management 60 (2017) 100–111

Fig. 4. FTIR spectra of recovered polymers from data cable.

associated with CAOAC vibration in ester linkage of PC. The Fig. 4(e) represents the molecular vibration spectra obtained
band at 1772 cm
1 was attributed to the C@O stretching vibra- from the bush used in the data cable. A broadband with two max-
tions of ester linkages. The sharp peaks at 1502 and 1013 cm
1 ima at 1054 and 1010 cm
1 corresponds to the SiAOASi backbone
recognized by the presences of aromatic ring in the PC molec- vibrations in silicon rubber. The SiAC bonds in the SiACH3 con-
ular structure, arises from aromatic in plane CAC stretch vibra- tributed another strong vibration peak at 782 cm
1. Mean while
tion and aromatic CAH deformation respectively. Similarly, strong peaks at 1254 and 2965 cm
1 represents CAH vibrations
peaks at 2968 and 1364 cm
1 corresponds to the methyl in alkyl (methyl (CH3)) bond present in the chemical structure of
(ACH3) vibrations in PC structure. silicon rubber (Zhang et al., 2012).
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 105

Table 1 3.4. Assessment of plasticizers content in recycled PVC

Density of recovered polymer from the data cable.

Sample Density (g/cm3) Sample Density (g/cm3) As the flexible PVC is widely used in the cable industry, most of
v-PC 1.211 Connector (PC) 1.213 them contain plasticizer or other organic additives in order to
v-PVC 1.320 Outer jacket (PVC) 1.473 improve its flexibility. The phthalic acid esters (phthalates) were
v-PE 0.871 Supporting cable (PE) 0.931 predominantly used in the PVC compounds because of its excellent
v-PE 0.871 Twisted wire (PE) 0.862 plasticizing properties (Mersiowsky et al., 2001). Similarly, struc-
v-Silicon rubber 1.120 Bush (Silicon rubber) 0.921
tural characteristics such as aromatic ring and ester linkage in
the phthalates make it possible for good interaction with the PVC
polymer chain (Daniels, 2009). The results from the GC–MS analy-
3.3. Density measurement of recovered polymer from data cable sis directs towards the use of various plasticizers in the r-PVC
cables which is evident from the total ion chromatogram and
The density of the different polymeric materials used in the data extracted ion chromatogram for phthalate (Fig. 5) obtained from
cables are represented in Table 1. All the polymeric material recov- the r-PVC. The major fragment measured in electron impact ionisa-
ered from the data cables shows deviated densities from their vir- tion is at 149 m/z as a result of the formation of a furan ring
gin polymeric material. The changes in the density value were through the loss of the alkyl ester group (Staples, 2003). The chro-
possibly due to additives added during previous formulation at matogram primarily contains phthalate plasticizers even though
the time of compounding. non phthalate plasticizers like tri(2-Ethylhexyl)trimellite were

Fig. 5. GC–MS chromatogram for plasticizers recovered from r-PVC.

106 S.S. Suresh et al. / Waste Management 60 (2017) 100–111

Table 2
Major plasticizers with its purity recovered from r-PVC.

Sl. no. Plasticizer Retention time Purity

1 12.76 81%

Diisobutyl phthalate (DIBP)

2 16.80 92%

Bis(2-ethylhexyl) phthalate
3 18.07 93%

Dioctyl terephthalate
4
CH3 24.80 90%

CH3

O O
H3 C O O
H3 C O CH3
O
CH3
Tri(2-Ethylhexyl) trimellitate

identified from the r-PVC. The major plasticizers present in the r- to the formation of various oxidation products containing carbonyl
PVC and its purity are given in Table 2. Other than plasticizers, a functional groups (Torikai and Hasegawa, 1999) as per the mecha-
peak at retention time (RT) 13.08 min present in the chro- nism shown in Fig. 6(b).
matogram shows the presence of palmitic acid, possibly leached As reported elsewhere (Quennehen et al., 2015) the vibrational
from the heat stabilizers used in the r-PVC product (Egbuchunam frequencies of phthalate were found to interfere with the charac-
et al., 2007). teristics vibration of PVC degradation spectra and hence they have
to be extracted before analysing the premature degradation of the
r-PVC. As r-PVC is completely soluble in THF, the r-PVC material
4. Previous life cycle degradation of recycled PVC was extracted with THF solvent to remove the plasticizer and other
components from it. The residue obtained after treating with
FTIR is a powerful analytical tool for structural analysis and pre- methanol was used for the FTIR-ATR analysis. Likewise, the r-PVC
vious degradation study of recycled materials. The degradation of obtained after the processing, was studied to figure out the degra-
PVC is initiated with unzipping of HCl molecule to form a double dation level during processing study. The obtained FTIR spectra
bond in the molecular structure of PVC. The CACl near to the was compared with the r-PVC material to understand level of the
formed double bond undergoes a free radical elimination of chlo- degradation during different situation.
rine. The eliminated chlorine radical abstracts the hydrogen atom FTIR spectra for identification of polyene sequences and car-
from the adjacent carbon as shown by the mechanism in Fig. 6 bonyl indices from r-PVC at different conditions were given in
(a). The eliminated HCl can further accelerate degradation of PVC Fig. 7. The presence of conjugated polyene sequences was identi-
polymer through the autocatalysis reaction. The random dechlori- fied from the peak at 1579 cm
1, which is the characteristics of
nation leads to formation of conjugated double bonds or polyene alkene structural vibration, formed after the unzipping of HCl.
sequence (Hao et al., 2016; Merah et al., 2013; Winkler, 1959; The band at 1720 cm
1 is attributed to the carbonyl (C@O) stretch-
Zaikov et al., 1998). ing vibration, which is possibly due to the oxidation product
Moreover, polyvinyl chloride chains undergo oxidation reaction formed during its ageing. Similarly, peak at 2916 cm
1 represent
in the presence of oxygen during its degradation as shown in the the CAH stretching vibration present in the r-PVC. The method
mechanism by Gardette et al. (1989). The oxygen molecules are involved is subtracting the transmission value of the peak of inter-
reacted with the alkyl radicals formed after abstraction of hydro- est (carbonyl stretching for carbonyl indices and polyene vibration
gen from the polymeric chains of PVC. The oxidation of PVC leads value for polyene sequences) from the base line value (TB) and
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 107

Fig. 6. Ageing mechanism of polyvinyl chloride.

dividing the obtained value with CAH stretching vibration value T B
T 1579
Polyene index ¼ ð2Þ
subtracted from the base line value (Arnold and Maund, 1999). T B
T 2916
Sombatsompop and Sungsanit (2003) used a similar method in
order to identify the carbonyl and polyene indices from the post The results in Table 3 suggest that the r-PVC contain polyene and
consumer PVC bottles and cables. The carbonyl index and conju- carbonyl indices are formed during its life cycle, is due to the unzip-
gated polyene indices can be calculated by employing the follow- ping of hydrogen chloride followed by the oxidation reaction. How-
ing relationships (1) & (2). ever, after the batch mixing of r-PVC at 165 °C there is a small
change in the polyene indices and carbonyl indices value. These
T B
T 1720
Carbonyl index ¼ ð1Þ results suggest that during the reprocessing there is a possibility
T B
T 2916 for degradation of molecular structure although the effect is
108 S.S. Suresh et al. / Waste Management 60 (2017) 100–111

function of time. Fig. 8(a) represents the torque–time curve for r-

PVC at 50 rpm and 165 °C. The temperature was set to 165 °C in
order to avoid further degradation. From the primary stage (0–
1 min) of curve, it can be seen that when polymer is introduced
into the chamber, there is a sharp increase in the torque curve pos-
sibly due to the resistance offered by the materials to the rotating
screws. This can be further explained by Fig. 8(b), which represents
the energy calculation during torque study based on the area under
the torque curve over the testing period. During initial period there
is a sharp increase in energy value. In the second stage (1–5 min),
there is a sudden drop in the torque value and an equilibrium value
is reached after 1 min and the value becomes consistent for a fur-
ther time period. The steady-state torque values attained in the
batch mixer is probably due to total heat transfer to the polymeric
material and complete melting of the material. After attaining
steady state, torque–time curve is less fluctuating and this beha-
viour shows complete homogeneous mixing of the polymeric
Fig. 7. FTIR spectra for the analysis of polyene and carbonyl indices. material.
Plasticizers present in the r-PVC plays an important role in tor-
que study. Depending on the type, nature and concentration of
Table 3 plasticizer used in the PVC, resulting properties may vary. Gener-
Polyene and carbonyl indices at different conditions of r-PVC. ally a mixture of plasticizers is used in PVC to improve its property
Index type r-PVC r-PVC after r-PVC after batch
(Daniels, 2009; Garcia et al., 2007; Gonzalez-Roa et al., 1991). In
extraction mixing order to understand the reprocessability of the r-PVC polymer
Polyene index (PI) 0.08 0.07 0.12
the torque value was compared (Fig. 8(a)) with the v-PVC polymer
Carbonyl index (CI) 1.7 1.5 1.9 material. In the case of v-PVC maximum torque value attained was
29.8 N m with an average value of 10.89 N m for a period of five
minutes. The r-PVC shows the maximum torque value of 28 N m,
however, the average torque value of the r-PVC was reduced to
negligible. The comparison results of r-PVC and r-PVC after extrac- 6 N m compared with V-PVC for the same period of time. The r-
tion with THF indicates 11.8% decrease in carbonyl index value than PVC shows 44.9% reduction in average torque value in contrast to
r-PVC, which may be due to the influence of vibration spectra of v-PVC. The low average torque value for r-PVC may be resulted
added additives. from the presence of previously added plasticizers in the r-PVC.
The presence of plasticizers reduces the melt viscosity of r-PVC,
4.1. Torque measurement study for recycled PVC which influences the torque value. Obviously, the same results
were reflected in the value of the energy curves (Fig. 8(b)) where
The ability to reprocess r-PVC compounds were assessed by the r-PVC energy curve is lower than the V-PVC. Further studies using
measurement of the torque level during blending in the batch GC–MS analysis confirms the presence of plasticizers in the r-PVC.
mixer. Batch mixers are useful in preparing small quantities of However, Table 3 shows minor amount of polyene and carbonyl
polymeric blends and provide information about torque as a indices values after reprocessing analysis, which is inadequate to

Fig. 8. Comparison of (a) torque measurement (b) energy curve of r-PVC with v-PVC.
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 109

be consider in mechanical recycling of r-PVC. Therefore, r-PVC

recovered from the data cables can be further reprocessed for
mechanical recycling procedures without affecting the chemical
structure of r-PVC.

4.2. Mechanical behaviour of r-PVC

Comparison of the tensile behaviour of v-PVC (Garcia et al.,

2007) with r-PVC is illustrated in Table 4. With regards to the v-
PVC, recycled PVC shows decline in tensile properties and this
points to the existence of a certain level of degradation in the
molecular structure of r-PVC. The decrease in the tensile behaviour
of r-PVC can be attributed to the restriction of polymer chain
movement, which may be due to the formation of shorter polymer
chain through chain breaking during ageing. Similarly elimination
of chlorine atom from the molecular structure of r-PVC during
degradation, results in fewer interaction of plasticizers with poly-
mer chain. Plasticizers present in the PVC matrix were interacted
via electrostatic interaction or dipole-dipole interactions with Fig. 10. DSC thermogram for r-PVC.
polar chlorine atom present in the PVC (Daniels, 2009).

thermal degradation. The maximum decomposition rate for the

4.3. Thermal analysis
initial degradation of r-PVC was observed at 271 °C. The second
stage degradation ranging from 425 to 500 °C corresponds to the
The decomposition of PVC begins at low temperature as com-
thermal cracking and decomposition of the PVC backbone after
pared to the other polymers such as PS, PET, PP, PE and the lower
the elimination of HCl. Polymer backbone is completely cracked
stability of PVC is due to the thermally liable structure (Yu et al.,
into carbon dioxide and water during this step. The maximum
2016). The two typical stages of thermal degradation in PVC can
decomposition rate for the second degradation is 472 °C for r-PVC.
be seen from the TGA curve (Fig. 9) of r-PVC. The first stage of
After the first stage of thermal degradation approximately 55%
degradation started approximately from 190 to 320 °C because of
weight loss occurs to the r-PVC sample. However, after the first
the dehydrocholorination from the PVC structure. During the ini-
stage of the degradation, DTG curve (Fig. 9) for r-PVC exhibit small
tial step of thermal decomposition complete elimination of HCl
peaks and inflexions that may correspond to the various compo-
has occurred from r-PVC leading to the formation of unsaturated
nents added to the PVC during its formulation. Approximately
hydrocarbons. Along with HCl, small amount of benzene, toluene,
22% weight loss occurs during the second thermal degradation of
naphthalene and alkylated benzene were also eliminated
r-PVC. Even after the completion of 700 °C of heating, only 77%
(Matuschek et al., 2000). However, chlorine is the major candidate
weight loss has occurred to the r-PVC and remaining 23% may pos-
completely removed from the polymer during the initial stage of
sibly be due to the inorganic additives and residues added to the
PVC.
Table 4 The DSC thermogram for r-PVC is shown in Fig. 10. The sample
Comparison of tensile behaviour of r-PVC and v-PVC. of r-PVC showed a single glass transition temperature (Tg) value at
Parameter Value 85.3 °C which can be ascribed to the mobility of the PVC polymeric
chain. On the other hand, for a recycled polymeric material, glass
v-PVC r-PVC
transition temperature varies with its parent polymers due to sev-
Tensile strength (MPa) 51.83 19.25 ± 0.2
eral factors like structural effects, molar mass, degree of cross-
Modulus (MPa) 1957 634 ± 8
Tensile strain (%) 77.4 24.99 ± 0.9 linking and previous degradative effect. The degradation of r-PVC
follow endothermic reaction pathway because the degradation of
PVC consist of eliminations and take place as the reverse of the
organic addition reaction across the double bond of alkenes
(Shnawa et al., 2015). The main DSC peak that appears at around
306 °C in DSC scan of r-PVC, represented the main degradation step
of r-PVC. Moreover, the r-PVC shows the value of 59.9 °C with HDT
measurement.

5. Conclusion

Plastic materials are extensively used in the cable products

because of its advantages like good insulating properties, easy pro-
cessability, low cost etc. PVC is the third most widely produced
synthetic plastic polymer after PE and Polypropylene (Bucur
et al., 2012). In the data cables used in computers PVC is the major
polymer present. Hence, considering the importance of PVC,
amount of PVC in data cables, easiness in isolating PVC from data
cables reprocessability of PVC material was studied. Data cables
also contain metals such as copper and steel and other polymers
Fig. 9. TGA and DTG curve of r-PVC. like PE, PC and silicon rubber in minor quantity. Even though PE
110 S.S. Suresh et al. / Waste Management 60 (2017) 100–111

is present in larger volume, the difficulties in isolating from cables Bucur, L., Sălăvăstru, C.M., Bucur, G., T ß iplica, G.S., 2012. Polyvinyl Resins. In:
Kanerva’s Occupational Dermatology. Springer, Berlin Heidelberg, pp. 1943–
hinder its recycling.
1950.
The plastic composition was analysed and confirmed using FTIR Buekens, A., Yang, J., 2014. Recycling of WEEE plastics: a review. J. Mater. Cycles
technique. Besides, density measurement also confirmed the poly- Waste Manage. 16 (3), 415–434.
mers, even though they show slight variation from density values Cano, J.M., Marın, M.L., Sanchez, A., Hernandis, V., 2002. Determination of adipate
plasticizers in poly (vinyl chloride) by microwave-assisted extraction. J.
of virgin polymers. The change in densities can be due to the pres- Chromatogr. A 963 (1), 401–409.
ence of additives in it. GC–MS analysis of the r-PVC collected from Daniels, P.H., 2009. A brief overview of theories of PVC plasticization and methods
the data cables were done and it confirmed the presence of differ- used to evaluate PVC-plasticizer interaction. J. Vinyl Addit. Technol. 15 (4), 219–
223.
ent plasticizers like Diisobutyl phthalate, Bis(2-ethylhexyl) phtha- de Araújo, M.C.P.B., Chaves, A.P., Espinosa, D.C.R., Tenório, J.A.S., 2008. Electronic
late and Dioctyl terephthalate. scraps – recovering of valuable materials from parallel wire cables. Waste
The carbonyl and polyene indices value calculation using FTIR Manage. 28 (11), 2177–2182.
Egbuchunam, T.O., Balköse, D., Okieimen, F.E., 2007. Effect of zinc soaps of rubber
spectra provided details about the premature degradation in the seed oil (RSO) and/or epoxidised rubber seed oil (ERSO) on the thermal stability
r-PVC. The reduced values for both indices are after extracting of PVC plastigels. Polym. Degrad. Stab. 92 (8), 1572–1582.
r-PVC with THF was due to the absence of plasticizers. Thereby Garcia, D., Balart, R., Sanchez, L., Lopez, J., 2007. Compatibility of recycled PVC/ABS
blends. Effect of previous degradation. Polym. Eng. Sci. 47 (6), 789.
interaction of AC@O groups from the plasticizers can be avoided Gardette, J.L., Gaumet, S., Lemaire, J., 1989. Photooxidation of poly (vinyl
by extracting plasticizers from r-PVC. chloride). 1. A reexamination of the mechanism. Macromolecules 22 (6),
Reprocessability studies of r-PVC using batch mixing confirm 2576–2581.
Gawade, A.R., Lodha, A.V., Joshi, P.S., 2007. PVC/ABS blends: thermal and
the recyclability of the polymer. The r-PVC shows reduced values
morphological studies. J. Macromol. B. 47 (1), 201–210.
for average torque and energy value in contrast with the v-PVC. Gonzalez-Roa, C., Ramos-Devalle, L.F., Sanchez-Adame, M., 1991. The fusion
The presence of plasticizers in r-PVC reduces the melt viscosity characteristics of PVC-plasticizer mixtures. J. Vinyl Technol. 13 (3), 160–164.
during processing time and its leads to lowering of torque value. Hao, Y.B., Hou, P., Li, G.X., Li, P., Qiu, F., He, H., Zeng, J.B., Wang, M., 2016. Effect of
base-deposited graphene oxide on the thermal stabilization of poly (vinyl
The r-PVC shows increased indices value after reprocessing study chloride). Polym. Int. 65 (1), 125–132.
possibly due to the amplified degradation in r-PVC chain. However, http://www.data-cabling-expert.tv/data-cabling-information-vault/13-types-of-
the degradation effect is considerably low for r-PVC after repro- data-cable (assessed on 05–October–2015).
Jadhao, P., Chauhan, G., Pant, K.K., Nigam, K.D.P., 2016. Greener approach for the
cessing analysis. The declined mechanical values indicate the pos- extraction of copper metal from electronic waste. Waste Manage. 57, 102–112.
sibility for chain degradation and polymer chain breaking of r-PVC Krimm, S., Folt, V.L., Shipman, J.J., Berens, A.R., 1963. Infrared spectra and
during the service period. assignments for polyvinyl chloride and deuterated analogs. J. Polym. Sci.
General Pap. 1 (8), 2621–2650.
The thermal behaviours of r-PVC was studied using TGA, DSC Lambert, F., Gaydardzhiev, S., Léonard, G., Lewis, G., Bareel, P.F., Bastin, D., 2015.
and HDT. Thermogravimetric analysis shows a two-stage degrada- Copper leaching from waste electric cables by biohydrometallurgy. Mineral Eng.
tion of r-PVC with maximum decomposition at 271 °C and 427 °C 76, 38–46.
Lee, J.S., Cho, K.C., Ku, K.H., Cho, G., Lee, J.H., 2012. Recyclable insulation material
respectively. The DSC thermogram obtained for r-PVC shows a based on polyethylene for power cable. In: Condition Monitoring and Diagnosis
single transition temperature at 85.3 °C. The main endothermic (CMD), 2012 International Conference on IEEE, pp. 88–90.
peak that appears at 306 °C represents the main degradation step Linde, E., Gedde, U.W., 2014. Plasticizer migration from PVC cable insulation – the
challenges of extrapolation methods. Polym. Degrad. Stab. 101, 24–31.
of r-PVC, which followed an endothermic pathway. In addition,
Matuschek, G., Milanov, N., Kettrup, A., 2000. Thermoanalytical investigations for
r-PVC shows a heat deflection temperature of 59.9 °C. the recycling of PVC. Thermochimi. Acta. 361 (1), 77–84.
The present study shows that, presence of additives such as Merah, N., Bazoune, A., Fazal, A., Khan, Z., 2013. Weathering degradation
plasticizers and premature degradation has an important effect mechanisms of chlorinated PVC. Int. J. Plast. Technol. 17 (2), 111–122.
Mersiowsky, I., Weller, M., Ejlertsson, J., 2001. Fate of plasticised PVC products
on the mechanical properties of the recycled materials. The under landfill conditions: a laboratory-scale landfill simulation reactor study.
mechanical properties of r-PVC were lower as compared with Water Res. 35 (13), 3063–3070.
v-PVC. Thus, in order to avail this r-PVC in some applications and Quennehen, P., Royaud, I., Seytre, G., Gain, O., Rain, P., Espilit, T., François, S., 2015.
Determination of the aging mechanism of single core cables with PVC
to bring an alternative to the WEEE disposal problems, its mechan- insulation. Polym. Degrad. Stab. 119, 96–104.
ical properties has to improve by some other methods. Hence, pro- Sadat-Shojai, M., Bakhshandeh, G.R., 2011. Recycling of PVC wastes. Polym.
posed future work will be melt blending of r-PVC with other Degrade. Stab. 96 (4), 404–415.
Sarath, P., Bonda, S., Mohanty, S., Nayak, S.K., 2015. Mobile phone waste
polymers recovered from the WEEE, to improve the mechanical management and recycling: views and trends. Waste Manage. 46, 536–545.
properties of r-PVC. Sheih, S.W., Tsai, M.S., 2000. Hot water separation process for copper and insulating
material recovery from electric cable waste. Waste Manage. Res. 18 (5), 478–
484.
Shi, W., Zhang, J., Shi, X.M., Jiang, G.D., 2008. Different photodegradation processes
Acknowledgement
of PVC with different average degrees of polymerization. J. Appl. Polym. Sci. 107
(1), 528–540.
The authors would like to thank Spectroscopy Division Indian Shnawa, H.A., Khalaf, M.N., Jahani, Y., Taobi, A.A.H., 2015. Efficient thermal
Institute of science, Bangalore, for GC/MS analysis and Department stabilization of polyvinyl chloride with tannin-Ca complex as bio-based
thermal stabilizer. Mater. Sci. Appl. 6 (05), 360.
of Chemicals and Petrochemicals, Government of India for the Soman, V.V., Kelkar, D.S., 2009. FTIR studies of doped PMMA-PVC blend system.
financial support. Thanks are extended to Sunita Mahapatra, M. Macromol. Sym. 27 (1), 152–161.
Tech-Plastic Engineering Technology scholar for her help in disas- Sombatsompop, N., Sungsanit, K., 2003. Processability, rheology, and thermal,
mechanical, and morphological properties of postconsumer poly (vinyl
sembly and sorting of waste PVC data cables. chloride) bottles and cables. J. Appl. Polym. Sci. 89 (10), 2738–2748.
Staples, C.A., 2003. Phthalate Esters: The Handbook of Environmental Chemistry.
Springer Publications.
References Stringer, R., Labunska, I., Santillo, D., Johnston, P., Siddorn, J., Stephenson, A., 2000.
Concentrations of phthalate esters and identification of other additives in PVC
children’s toys. Environ. Sci. Pollut. Res. 7 (1), 27–36.
Arnold, J.C., Maund, B., 1999. The properties of recycled PVC bottle compounds. 2:
Tanskanen, P., 2013. Management and recycling of electronic waste. Acta Materialia
Reprocessing stability. Polym. Eng. Sci. 39 (7), 1242–1250.
61 (3), 1001–1011.
ASTM Committee D-20 on Plastics. Section D20. 70.01, 1991. Standard Test Methods
Torikai, A., Hasegawa, H., 1999. Accelerated photodegradation of poly (vinyl
for Density and Specific Gravity (Relative Density) of Plastics by Displacement.
chloride). Polym. Degrad. Stab. 63 (3), 441–445.
American Society for Testing and Materials.
Unger, N., Gough, O., 2008. Life cycle considerations about optic fibre cable and
Awasthi, A.K., Zeng, X., Li, J., 2016. Environmental pollution of electronic waste
copper cable systems: a case study. J. Clean. Prod. 16 (14), 1517–1525.
recycling in India: a critical review. Environ. Pollut. 211, 259–270.
Wath, S.B., Dutt, P.S., Chakrabarti, T., 2011. E-waste scenario in India, its
Brebu, M., Vasile, C., Antonie, S.R., Chiriac, M., Precup, M., Yang, J., Roy, C., 2000.
management and implications. Environ. Monit. Assess. 172 (1–4), 249–262.
Study of the natural ageing of PVC insulation for electrical cables. Polym.
Degrad. Stab. 67 (2), 209–221.
 S.S. Suresh et al. / Waste Management 60 (2017) 100–111 111

Winkler, D.E., 1959. Mechanism of polyvinyl chloride degradation and stabilization. Zaikov, G.E., Gumargalieva, K.Z., Pokholok, T.V., Moiseev, Y.V., 1998. PVC wire
J. Polym Sci. 35 (128), 3–16. coatings: Part l – ageing process dynamics. Int. J. Polym. 39 (1–2), 79–125.
Yang, L., Hu, Y., You, F., Chen, Z., 2007. A novel method to prepare zinc Zhang, H., Tu, Y., Lu, Y., Xu, Z., Chen, C., Xie, L., 2012. Study on aging
hydroxystannate-coated inorganic fillers and its effect on the fire properties characteristics of silicone rubber insulator sheds using FTIR. In: Electrical
of PVC cable materials. Polym. Eng. Sci. 47 (7), 1163–1169. Insulation (ISEI), Conference Record of the 2012 IEEE International
Yu, J., Sun, L., Ma, C., Qiao, Y., Yao, H., 2016. Thermal degradation of PVC: a review. Symposium on IEEE. 83–86.
Waste Manage. 48, 300–314. Zhang, Y., Xu, Y., Song, Y., Zheng, Q., 2013. Study of poly (vinyl chloride)/
Zabłocka-Malicka, M., Rutkowski, P., Szczepaniak, W., 2015. Recovery of copper acrylonitrile–styrene–acrylate blends for compatibility, toughness, thermal
from PVC multiwire cable waste by steam gasification. Waste Manage. 46, stability and UV irradiation resistance. J. Appl. Polym. Sci. 130 (3), 2143–2151.
488–496. Zhao, W., Siew, W.H., Given, M.J., 2013. The electrical performance of thermoplastic
Zackrisson, M., Christina, J., 2014. Life cycle assessment and life cycle cost of waste polymers when used as insulation in cables. In: Power Engineering Conference
management—plastic cable waste. Adv. Chem. Eng. Sci. 4, 221–232. (UPEC) on IEEE, pp. 1–4.